Boron-containing cyclic release compound and color-changing film containing the same

Abstract

The present disclosure relates to novel photoluminescent complexes comprising a BODIPY moiety covalently attached to a blue-light absorbing xanthenoisoquinoline derivative, and color conversion films and backlight units employing the same.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority to U.S. Provisional Patent Application No. 63 / 152,301, filed on 22 February 2021, which in whole constitutes part of this specification by reference. [Background technology]

[0002] In color reproduction, gamut, or color space, is a specific, complete subset of colors available on a device such as a television or monitor. For example, Adobe® Red, Green, Blue (RGB) is a wide-gamut color space achieved by using pure spectral primary colors. It was developed to provide a wider color space and a more realistic representation of visible colors seen through a display. It is believed that devices capable of providing a wider color gamut can enable displays to depict more vibrant colors.

[0003] As high-definition, large-screen displays become commonplace, there is a growing demand for higher-performance, thinner, and more feature-rich displays. Current light-emitting diodes (LEDs) produce a white light source by exciting a green, red, or yellow phosphor with a blue light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is very large, usually exceeding 40 nm, resulting in overlapping of the green and red spectra, leading to color rendering where they cannot be completely distinguished from each other. This overlap leads to low color rendering and a reduced color gamut.

[0004] To compensate for the reduction in color gamut, a method has been developed that uses films containing quantum dots in combination with LEDs. However, there are problems with the use of quantum dots. Firstly, cadmium-based quantum dots are extremely toxic and have been banned in many countries due to health and safety concerns. Secondly, non-cadmium-based quantum dots have very low efficiency in converting blue LED light into green and red light. Thirdly, quantum dots require an expensive encapsulation process to protect them from moisture and oxygen. Finally, the cost of using quantum dots is high because it is difficult to control size uniformity during the manufacturing process.

[0005] Therefore, there is a need to improve the performance of color conversion films, backlight units, and display devices. [Overview of the project]

[0006] The photoluminescent complexes described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other devices that utilize color displays. The photoluminescent complexes of this disclosure provide novel color-converting dye complexes having good blue light absorption and a narrow emission bandwidth, with an emission bandwidth full width at half maximum (FWHM) of less than 40 nm. In some embodiments, the photoluminescent complex absorbs light of a first wavelength and emits light of a second wavelength higher than the first wavelength. The photoluminescent complexes disclosed herein can be used in color-converting films used in light-emitting devices. The color-converting films of this disclosure provide high color rendering by reducing color degradation by reducing overlap in the color spectrum.

[0007] In some embodiments, the photoluminescent complex may comprise a blue light-absorbing xanthenoizoquinoline derivative, a linker complex comprising an optionally substituted ester or substituted ether, and a boron-dipyromethene (BODIPY) moiety. In some embodiments, the linker complex can covalently bond the xanthenoizoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoizoquinoline derivative absorbs light of a first excitation wavelength and transfers the energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs energy from the xanthenoizoquinoline derivative and emits light energy of a second, higher wavelength. In some embodiments, the photoluminescent complex has an emission quantum yield of more than 80%.

[0008] In some embodiments, the photoluminescent complex may have an emission band with a full width at half maximum (FWHM) of up to 40 nm.

[0009] In some embodiments, the photoluminescent complex may have a Stokes shift of 45 nm or more, which is the difference between the excitation peak of the blue light absorption portion and the emission peak of the BODIPY portion.

[0010] In some embodiments, the xanthenoizoquinoline derivative is given by the following general formula: [ka] (In the formula, R 0 and R 10 This can independently be hydrogen (H), a C1-C4 alkyl group, or an optionally substituted aryl group.

[0011] In some embodiments, the BODIPY portion is expressed by the following general formula: [ka] (In the formula, R1 , R 2 , R 3 , R 4 , R 5 , R 6 may independently be selected from a hydrogen atom (H), a C1-C3 alkyl group, an optionally substituted aryl group, or an ether group. In some embodiments, R 7 , R 8 , and R 9 may independently be selected from a hydrogen atom (H), a methyl group (-CH3), or -Cl.

[0012] Some embodiments include a color conversion film. In some examples, the color conversion film may include a color conversion layer including a resin matrix and at least one photoluminescence complex described herein dispersed within the resin matrix. In some embodiments, the color conversion film may have a thickness between about 1 μm and about 200 μm. In some embodiments, the color conversion film of the present disclosure can absorb blue light in a wavelength range from about 400 nm to about 480 nm and emit light in a wavelength range from about 510 nm to about 560 nm. In another embodiment, a color conversion film is included that can absorb blue light in a wavelength range from about 400 nm to about 480 nm and emit light in a wavelength range from about 575 nm to about 645 nm. In some embodiments, the color conversion film may further include a transparent substrate layer. In some embodiments, the transparent substrate layer has two opposing surfaces, and the color conversion layer is disposed on one of the opposing surfaces.

[0013] Some embodiments include a method of making a color conversion film. In some embodiments, the method includes dissolving the aforementioned photoluminescence complex and binder resin in a solvent and applying the mixture to one of the opposing surfaces of a transparent substrate.

[0014] Some embodiments include a backlight unit including the color conversion film described herein.

[0015] Some embodiments include display devices comprising the backlight unit described herein.

[0016] This application provides a photoluminescent complex having excellent color gamut and luminescence characteristics, a method for manufacturing a color conversion film using the photoluminescent complex, and a backlight unit comprising the color conversion film. These embodiments and other embodiments are described in detail below. [Brief explanation of the drawing]

[0017] [Figure 1] This graph shows the absorption and emission spectra of one embodiment of the photoluminescent complex (PLC-1). [Figure 2] This graph shows the absorption and emission spectra of one embodiment of the photoluminescent complex (PLC-2). [Figure 3] This graph shows the absorption and emission spectra of one embodiment of the photoluminescent complex (PLC-4). [Figure 4] This graph shows the absorption and emission spectra of one embodiment of the photoluminescent complex (PLC-5). [Modes for carrying out the invention]

[0018] This disclosure relates to photoluminescent compounds and complexes used in color conversion films, backlight units, and display devices.

[0019] In some embodiments, the disclosure includes photoluminescent complexes and their use in color conversion films. Photoluminescent complexes can be used to improve and enhance the transmission of one or more desired emission bandwidths within a color conversion film. In some embodiments, a photoluminescent complex can also enhance the transmission of a desired first emission bandwidth while reducing the transmission of a second emission bandwidth. For example, a color conversion film can enhance the contrast or intensity between two or more colors, improving their distinguishability from one another. The disclosure describes photoluminescent complexes that can enhance the contrast or intensity between two colors, improving their distinguishability from one another.

[0020] Where a compound or chemical structure is referred to as “substituted” as used herein, this means it may include one or more substituents. A substituted compound is derived from an unsubstituted parent structure in which one or more hydrogen atoms on the parent structure are independently replaced by one or more substituents. The parent structure may have one, two, three, or more substituents. In some embodiments, the substituent(s) may be independently selected from optionally substituted alkyl, alkenyl, or C3-C7 heteroalkyl groups.

[0021] The alkyl moiety may be branched, linear (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety may have 1 to 8 carbon atoms. Alkyl groups of compounds specified herein may be designated as "C1-C8 alkyl" or similar designations. As merely an example, "C1-C8 alkyl" indicates that the alkyl chain contains 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomers thereof. Thus, C1-C8 alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl, C1-C6 alkyl, C1-C7 alkyl, and C1-C8 alkyl. Alkyl groups may be substituted or unsubstituted. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0022] As used herein, the term "heteroalkyl" refers to an alkyl group, as defined herein, in which one or more constituent carbon atoms are replaced by nitrogen, oxygen, or sulfur atoms. Examples include, but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, and -CH2-CH2-S(O)-CH3. In some embodiments, up to two heteroatoms may be consecutive, for example, -CH2-NH-O-CH3.

[0023] The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 (where n is an integer) π-electrons. Aromatic rings can be formed from 5, 6, 7, 8, 9, or 10 or more atoms. Aromatic rings may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl or naphthyrenyl) and heterocyclic aryl (i.e., "heteroaryl" or "heteroaromatic") groups (e.g., pyridine). The term includes monocyclic or fused polycyclic (i.e., rings sharing pairs of adjacent carbon atoms) groups.

[0024] As used herein, the term "aryl" refers to an aromatic ring in which each of the ring-forming atoms is a carbon atom. An aryl ring may be formed by five, six, seven, eight, or nine or more carbon atoms. The aryl group may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthalenyl, and phenantrenyl.

[0025] The term "aralkyl" refers to an alkyl radical, as defined herein, that is substituted with an aryl group. Non-limiting aralkyl groups include benzyl and phenethyl.

[0026] As used herein, the term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0027] As used herein, the terms “bond,” “bonded,” “direct bond,” or “single bond” mean a chemical bond between two atoms or between two parts where the atoms joined by the bond are considered to be part of a larger structure.

[0028] As used herein, the term “part” refers to a specific segment or functional group of a molecule. A chemical part is often perceived as a chemical component embedded within or added to a molecule.

[0029] The term "ester" refers to a chemical moiety having the formula -COOR (wherein R is an alkyl, cycloalkyl, aryl, heteroaryl (linked via a ring carbon), or heterocyclic (linked via a ring carbon) moiety). Any hydroxyl or carboxyl moiety of the compounds described herein may be esterified. Any suitable method or procedure may be employed to prepare any ester derivative.

[0030] As used herein, the term "BODIPY" is defined by the following formula: [ka] This refers to the chemical part that possesses the characteristic feature.

[0031] The BODIPY portion may consist of a dipyromethene structure complexed with a disubstituted boron atom, typically a BF2 unit. The IUPAC name for the BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene.

[0032] As used herein, the terms "xanthenoisoquinoline," "xanthenoisoquinoline derivative," or "XI derivative" refer to the formula: [ka] This refers to a chemical part having a specific characteristic, such as 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione.

[0033] This disclosure relates to a photoluminescent complex that absorbs light energy at a first wavelength and emits light energy at a second, higher wavelength. The photoluminescent complex of this disclosure comprises an absorber-emitting portion and an emitter-emitting portion coupled via a linker, the distance between them being optimized so that the absorber-emitting portion transfers its energy to an acceptor-emitting portion, which then emits energy at a second wavelength greater than the absorbed first wavelength.

[0034] In some embodiments, the photoluminescent complex comprises a blue light-absorbing xanthenoizoquinoline derivative (XI derivative), a linker complex, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker complex may covalently bond the xanthenoizoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoizoquinoline derivative absorbs light of a first excitation wavelength, transferring energy to the BODIPY moiety, which then emits light energy of a second wavelength, the second wavelength of which is higher than the first (absorbed) wavelength. The energy transfer from the excited xanthenoizoquinoline derivative to the BODIPY moiety is thought to occur via Forster resonance energy transfer (FRET). This idea is based on the absorption / emission spectra of the photoluminescent complex, which have two main absorption bands: one in the blue light absorption band (xanthenoizoquinoline derivatives) and the other in the BODIPY absorption band, with only one emission band at the emission wavelength of the BODIPY portion (see Figures 1, 2, 3, and 4).

[0035] In some embodiments, the photoluminescent complex may have a high emission quantum yield. In some examples, the emission quantum yield may exceed 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield may exceed 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. The emission quantum yield can be measured by dividing the number of emitted photons by the number of absorbed photons, which is equal to the emission efficiency of the emission portion. In some embodiments, the absorption emission portion may have an emission quantum yield of more than 80%. In some embodiments, the quantum yield may be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), or 0.95 (95%), and may be close to 1 (100%). Quantum yield measurements in the film can be performed using a spectrophotometer, such as the Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, California, USA).

[0036] In some embodiments, the photoluminescent complex has an emission band with a full width at half maximum (FWHM) of less than 40 nm. FWHM is the width of the emission band in nanometers at an emission intensity that is half the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has FWHM values ​​for emission bands of about 35 nm or less, about 30 nm or less, about 25 nm or less, or about 20 nm or less.

[0037] In some embodiments, the photoluminescent complex may have a Stokes shift of 45 nm or greater. As used herein, the term "Stokes shift" means the distance between the excitation peak of the blue light absorption moiety and the emission peak of the BODIPY moiety.

[0038] The photoluminescent complexes of this disclosure may have a tunable emission wavelength. By incorporating certain substituents into the BODIPY moiety, the emission wavelength can be tuned to a wavelength between approximately 610 nm and approximately 645 nm.

[0039] In some embodiments, the blue light absorbing portion may have a peak absorption maximum wavelength between approximately 400 nm and approximately 470 nm. In some embodiments, the peak absorption wavelength may be any wavelength between approximately 400 nm and approximately 405 nm, approximately 405 nm and approximately 410 nm and approximately 415 nm, approximately 415 nm and approximately 420 nm and approximately 425 nm, approximately 425 nm and approximately 430 nm and approximately 435 nm, approximately 435 nm and approximately 440 nm and approximately 445 nm, approximately 445 nm and approximately 450 nm and approximately 455 nm, approximately 455 nm and approximately 460 nm and approximately 465 nm and approximately 470 nm, or within a range limited by any of these values.

[0040] In some embodiments, the photoluminescent complex may have an emission peak wavelength of approximately 610 nm to approximately 645 nm, approximately 610 nm to 615 nm, approximately 615 nm to 620 nm, approximately 620 nm to 625 nm, approximately 625 nm to 630 nm, approximately 630 nm to 635 nm, approximately 635 nm to 640 nm, approximately 640 nm to 645 nm, or any wavelength within the range limited by any of these values.

[0041] The photoluminescent complexes of this disclosure comprise a blue light-absorbing xanthenoizoquinoline derivative, a linker complex, and a BODIPY moiety. The linker complex covalently bonds the blue light-absorbing xanthenoizoquinoline derivative and the emitting BODIPY moiety. In some embodiments, the xanthenoizoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, which absorbs energy from the xanthenoizoquinoline derivative and emits light energy at a second, higher wavelength. In some embodiments, the photoluminescent complex has an emission quantum yield of more than 80%. In some embodiments, the photoluminescent complex is constructed such that the spatial distance between the blue light-absorbing xanthenoizoquinoline derivative and the BODIPY moiety is optimized via the linker complex. In some cases, the transfer of energy from the blue light-absorbing xanthenoizoquinoline derivative to the BODIPY moiety can be tuned to optimize the quantum yield of the photoluminescent complex.

[0042] Some embodiments include a blue light absorbing xanthenoizoquinoline derivative (XI derivative), the blue light absorbing xanthenoizoquinoline derivative having the following general formula: [ka] For example, it could be 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, where R 0 and R 10 This can be selected from a hydrogen atom (H), a methyl group, or an optionally substituted aryl group. In some embodiments, the optionally substituted aryl group may be a substituted phenyl group or a benzyl group.

[0043] In some embodiments, R 0 and / or R 10 The optionally substituted aryl group can be substituted with a trifluoromethyl group. In some embodiments, the optionally substituted aryl is 3,5-bis(trifluoromethyl)phenyl: [ka] It is possible.

[0044] In some embodiments, R 0 and / or R 10 The optionally substituted aryl is 4-trifluromethylphenyl: [ka] It is possible.

[0045] In some embodiments, R 0 and / or R 10 The arbitrarily substituted aryl is, [ka] It is possible.

[0046] The linker complex covalently bonds the blue-absorbing xanthenoizoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex can be adjusted to optimize the spatial distance between the blue-absorbing xanthenoizoquinoline derivative and the BODIPY moiety. By optimizing the spatial distance between the xanthenoizoquinoline derivative and the BODIPY, the quantum yield can be optimized. In some embodiments, the distance separating the blue-absorbing xanthenoizoquinoline derivative and the BODIPY moiety may be about 8 Å or greater.

[0047] In some embodiments, the linker complex of the photoluminescent complex covalently bonds the blue light-absorbing xanthenoizoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex may include a single bond between the xanthenoizoquinoline derivative and the BODIPY moiety.

[0048] In some embodiments, the linker complex may contain optionally substituted ester groups. In some examples, the linker may contain optionally substituted ether groups. In some embodiments, the linker complex may contain both optionally substituted ester groups and optionally substituted ether groups. In some embodiments, the linker complex may contain optionally substituted C2-C7 ester groups. When the linker complex contains substituted ester groups, the linker complex has the following structure: [ka] You can choose from the following options.

[0049] In some embodiments, the linker complex may contain an unsubstituted ester group. When the linker complex contains an unsubstituted ester group, the linker complex has the following structure: [ka] It is one of them.

[0050] In some embodiments, the linker complex may contain optionally substituted C2-C5 ether groups. When the linker complex contains optionally substituted ether groups, the linker complex is [ka] (wherein n can be 2, 3, 4, or 5)

[0051] In some embodiments, the linker composite is [ka] (wherein n is 1, 2, or 3)

[0052] In some embodiments, the linker composite is [ka] (wherein n is 1, 2, or 3)

[0053] In some embodiments, the linker composite is [ka] (wherein n is 1, 2, or 3)

[0054] In some embodiments, the linker composite is [ka] (wherein n is 1, 2, or 3)

[0055] In some embodiments, the linker composite is [ka] (wherein n is 1, 2, or 3)

[0056] In some embodiments, the linker composite is [ka] It is possible.

[0057] Several embodiments are given by the following general formula: [ka] It contains a BODIPY derivative having the following properties.

[0058] In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 R is independently selected from a hydrogen atom (H), a C1-C3 alkyl group, or an optionally substituted aryl or ether group. In some embodiments, R 7 , R8 , and R 9 This can be independently selected from a hydrogen atom (H), a methyl group (-CH3), or -Cl.

[0059] The BODIPY portion of this disclosure is R 3 and R 4 The BODIPY moiety may each be an aryl group, for example, a phenyl group. In some embodiments, R 1 , R 2 , R 5 and / or R 6 These are independently a hydrogen atom (H), a substituted aryl group, for example, a phenyl group ( [ka] ), diphenyl group (for example, [ka] ) and / or C2~C 10 Diphenyl groups having alkyl ether groups (for example, [ka] ) is possible.

[0060] The photoluminescent complexes of this disclosure can be represented by the following, which are provided for illustrative purposes only and should not be construed as limiting: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] Or a combination of those.

[0061] Some embodiments include a color conversion film comprising a resin matrix and a color conversion layer comprising one or more photoluminescent complexes described herein dispersed within the resin matrix.

[0062] Some embodiments include a color conversion film that may have a thickness of about 1 μm to about 200 μm. In some embodiments, the color conversion film may have a thickness of about 1 μm to 5 μm, about 5 μm to 10 μm, about 10 μm to 15 μm, about 1 μm to 20 μm, about 20 μm to 40 μm, about 40 μm to 80 μm, about 80 μm to 120 μm, about 120 μm to 160 μm, about 160 μm to 200 μm, or any thickness limited by any of these ranges.

[0063] In some embodiments, the color conversion film can absorb light in the wavelength range of approximately 400 nm to approximately 480 nm and emit light in the wavelength range of approximately 610 nm to approximately 645 nm.

[0064] In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, where the color conversion layer is positioned on the surface of the transparent layer adjacent to the light source and may be in physical contact with it. The transparent substrate is not particularly limited, and those skilled in the art will be able to select a suitable transparent substrate. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (polymethyl methacrylate), CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (glycol-modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cycloolefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the above resins can be used individually or in combination to provide a transparent substrate layer.

[0065] In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color-converting film may be placed on one of the opposing surfaces and be in physical contact with it. In some embodiments, the surface of the transparent substrate on which the color-converting film is not placed may be adjacent to a light source. In some examples, the substrate may function as a support during the fabrication of the color-converting film. The type of substrate used is not particularly limited, and the material and / or thickness is not limited as long as it is transparent and can function as a support. Any suitable substrate material and thickness may be used as the support substrate.

[0066] Some embodiments include a method for producing a color-converting film, the method comprising dissolving a photoluminescent compound and a binder resin described herein in a solvent and applying the mixture to the surface of a transparent substrate.

[0067] Examples of binder resins that can be used with photoluminescent complexes (sometimes multiple complexes) include acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and their saponification products, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinylphosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfones, nylon, cellulose resins, and cellulose acetate resins. In some embodiments, the binder resin may be a polyester resin and / or an acrylic resin.

[0068] In some embodiments, solvents that can be used to dissolve or disperse the photoluminescent complex and resin include alkanes, e.g., butane, pentane, hexane, heptane, and octane; cycloalkanes, e.g., cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, e.g., ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves®, e.g., Methyl Cellosolve®, Ethyl Cellosolve®, Butyl Cellosolve®, Methyl Cellosolve® acetate, and Ethyl Cellosolve® acetates, propylene glycols and their derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone; ethers, such as dioxane and tetrahydro Examples include furans, esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate, halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and cresol, and highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0069] Some embodiments include a backlight unit, which may comprise the aforementioned color conversion film.

[0070] Other embodiments may describe display devices that may include the backlight unit described herein.

[0071] Unless otherwise specified, all figures used herein and in the embodiments to describe properties such as the amount of components, molecular weight, and reaction conditions should be understood in all cases to be modified by the term "approximately." Therefore, unless otherwise specified, the numerical parameters shown herein and in the accompanying embodiments are approximations that may vary depending on the desired properties to be obtained, at least not as an attempt to limit the application of the doctrine of equivalents. Within the scope of the embodiments, each numerical parameter should be interpreted at least by applying common rounding techniques in light of the reported number of significant figures.

[0072] With respect to the disclosed processes and / or methods, the functions performed in the processes and methods may be implemented in various orders, as may be indicated by the context. Furthermore, the outlined steps and operations are presented as examples only, and some steps and operations may be optional, combined into fewer steps and operations, or extended into additional steps and operations.

[0073] This disclosure may occasionally describe different components that are contained within or linked to other different components. Such represented configurations are merely illustrative, and many other configurations can be realized to achieve the same or similar functions.

[0074] In general, the terms used in this disclosure and the accompanying embodiments (e.g., the text of the accompanying embodiments) are intended to be “open” terms (for example, the term “including” should be interpreted as “including, but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes, but not limited to,” etc.). Furthermore, where a specific number of elements are introduced, this can be interpreted as meaning at least the number stated, as may be indicated by the context (for example, the literal statement of “two statements” without other modifiers means at least two statements of two or more statements). Any disjunctions and / or disjunctions that, when used in this disclosure, represent two or more alternative terms should be understood to construed as construing the possibility of including one of the terms, either of the terms, or both of the terms. For example, the phrase "A or B" would be understood to include the possibilities of "A" or "B" or "A and B".

[0075] In the context describing this disclosure (particularly in the context of the embodiments described below), singular terms ("a", "an", "the") and similar reference subjects should be construed to include both singular and plural forms unless otherwise specifically indicated herein or unless the context clearly contradicts this interpretation. The use of any examples or representative phrases provided herein (e.g., "such as") is intended solely to better illustrate this disclosure and does not imply any limitation on the scope of any embodiment. The language herein should not be construed as indicating any unexpressed elements essential to the implementation of this disclosure.

[0076] The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Members of each group may be referenced and embodied individually or in any combination with other members of the group or other elements found herein. For convenience, it is anticipated that one or more members of a group may be included in or removed from a group. If such inclusion or removal occurs, this specification will include the modified groups and will therefore satisfy the description of all Markush groups used in the accompanying embodiments.

[0077] Certain embodiments described herein include the best mode known to the inventors for carrying out the disclosure. Naturally, variations of these described embodiments will be apparent to those skilled in the art by reading the above description. The inventors anticipate that those skilled in the art will use such variations as needed, and they intend that the disclosure will be carried out in ways other than those specifically described herein. Thus, embodiments include all variations and equivalents of the subject matter described in the embodiments, as permitted by applicable law. Furthermore, unless otherwise specifically indicated herein, or unless it is clearly inconsistent with the context, all combinations of the above elements in all possible variations are contemplated. Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other variations that may be used are within the scope of the embodiments. Thus, alternative embodiments may be used, for example, in accordance with the teachings herein, but not limited thereto. Thus, embodiments are not limited to those strictly shown and described.

[0078] Embodiment 1. A photoluminescent complex, Blue light absorbing xanthenoizoquinoline derivative, Linker complexes that are unsubstituted or substituted esters, The boron-dipyromethene (BODIPY) part, Includes, A photoluminescent complex in which a linker complex covalently bonds a xanthenoizoquinoline derivative and a BODIPY moiety, the xanthenoizoquinoline derivative absorbs light energy of a first excitation wavelength and transfers the energy to the BODIPY moiety, the BODIPY moiety absorbs energy from the xanthenoizoquinoline derivative and emits light energy of a second, higher wavelength, and the photoluminescent complex has an emission quantum yield of over 80%.

[0079] 2. Xanthenoisoquinoline derivatives have the general formula: 3. [ka] (In the formula, R 0 The photoluminescent complex of Embodiment 1, wherein ( is a bond, H, a C1-C3 methyl group, or an optionally substituted aryl group).

[0080] 4. The BODIPY part is a general formula: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 These are independently selected from bonds, H, C1-C3 alkyl, aryl and / or ethers. R 7 , R 8 , and R 9 The photoluminescent complex of Embodiment 1, wherein (which can be independently selected from a bond, H, or a methyl group (-CH3)).

[0081] 5.R 3 and R 4 However, each could be an aryl group, for example, a phenyl group. A photoluminescent complex of Embodiment 4.

[0082] 6. The photoluminescent complex of Embodiment 5, wherein the aryl group may be a phenyl group.

[0083] 7. Substituting aryl group is a phenyl group ( [ka] ), or diphenyl group ( [ka] A photoluminescent complex of Embodiment 4, which may be a result of this embodiment.

[0084] 8. The ether group is a C2-C10 alkyl ether group ( [ka] A photoluminescent complex of Embodiment 4, which may be a result of this embodiment.

[0085] 9. The linker, [ka] A photoluminescent complex of Embodiment 1, which can be selected from the following.

[0086] 10. Unsubstituted ester linkers, [ka] The photoluminescent complex of Embodiment 1.

[0087] 11. The substituted ester of the linker complex has the following structure: [ka] One of these is the photoluminescent complex of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11.

[0088] 12. The photoluminescent complex has the following structure: [ka] [ka] [ka] or a combination thereof One of them is the photoluminescent complex of Embodiment 1.

[0089] 13. A color conversion film, A transparent substrate layer, A color conversion layer containing a resin matrix, A photoluminescent complex comprising at least one photoluminescent compound of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, in which one photoluminescent compound is dispersed in a resin matrix, Color conversion film, including

[0090] 14. A color conversion film of embodiment 13, further comprising a singlet oxygen quenching agent.

[0091] 15. A color conversion film of embodiment 13, further comprising a free radical scavenger.

[0092] 16. The color conversion film of Embodiment 13, wherein the film has a thickness between 10 μm and 200 μm.

[0093] 17. The color conversion film of Embodiment 13, wherein the film absorbs light in the wavelength range of approximately 400 nm to approximately 480 nm and emits light in the wavelength range of 575 nm to approximately 645 nm.

[0094] 18. A method for producing a color conversion film, Dissolving the photoluminescent complex and binder resin of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 in a solvent, Applying the mixture to one of the opposing surfaces of a transparent substrate, Methods that include...

[0095] 19. A backlight unit including the color conversion film of Embodiment 13.

[0096] 20. A display device including the backlight unit of Embodiment 19. [Examples]

[0097] The embodiments of photoluminescent complexes described herein have been found to have improved performance compared to other forms of dyes used in color conversion films. These advantages are further demonstrated by the following examples, which are intended solely to illustrate the disclosure and are not intended to limit the scope or fundamental principles.

[0098] Example 1.1 Comparative example 1 (CE-1): [ka]

[0099] CE-1: 0.75 g of 4-hydroxyl-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Next, one drop of trifluoroacetic acid was added. The solution was stirred overnight at room temperature under an argon gas atmosphere. DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (2.0 g) was added to the resulting solution, and the mixture was stirred overnight. The next day, the solution was filtered and washed with dichloromethane to obtain dipyrrolemethane (1.9 g). Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution, and it was degassed for 10 minutes. After degassing, 5 mL of trifluoroboron-diethyl ether was slowly added, and the mixture was subsequently heated at 70°C for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to obtain 0.9 g of an orange solid (76% yield). LCMS(APCI+):C 21 H 24 Calculated value (M+H) for BF2N2O: 369; measured value: 369. 1H NMR (400MHz, chloroform-d): δ 6.64(s,2H), 5.97(s,2H), 4.73(s,1H), 2.56(s,6H), 2.09(s,6H), 1.43(s,6H).

[0100] Example 1.2 Comparative Example 2 (CE-2) was synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008.

[0101] Example 2: Synthesis of photoluminescent complexes: Synthesis of compound PLC-1: [ka]

[0102] Compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1): To a solution of lithium diisopropylamide (LDA) (2.00 M, 176 mL, 1.50 equivalents) in tetrahydrofuran (THF) (300 mL), compound 1-(4-bromophenyl)ethane-1-one (70.1 g, 352 mmol, 1.50 equivalents) was added at -78°C and the mixture was stirred at -78°C for 30 minutes. Compound (E)-(2-nitrovinyl)benzene (35.0 g, 235 mmol, 1.00 equivalent) was added to this mixture and the mixture was stirred at -78°C for 1 hour. Thin-layer chromatography (TLC) (petroleum ether:ethyl acetate = 5:1) showed that compound (E)-(2-nitrovinyl)benzene was consumed and a new spot was formed. The reaction mixture was quenched with 200 mL of aqueous NH4Cl solution at -70°C, extracted with 600 mL (200 mL x 3) of ethyl acetate (siRNA), dried over Na2SO4, filtered, and concentrated under reduced pressure to obtain the residue. The residue was purified by column chromatography (SiO2, petroleum ether / ethyl acetate = 1 / 0 → 5 / 1). Compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1) (40.0 g, 115 mmol, 48.9% yield) was obtained as a white solid, and this was... 1 Confirmed by HNMR. 1 HNMR:(400MHz,MeOD):δ 7.95~7.78(m,2H), 7.70~7.63(m,2H), 7.38~7.28(m,4H), 7.28~7.19(m,1H), 4.97 ~4.88(m,1H), 4.83~4.74(m,1H), 4.22~4.10(m,1H), 3.51(dq,J=7.0,17.5Hz,2H).

[0103] Compound 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2): A mixture of compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1) (40.0 g, 115 mmol, 1.00 equivalent), sulfur (11.1 g, 345 mmol, 3.00 equivalent), NH4OAc (53.1 g, 689 mmol, 6.00 equivalent), and morpholine (30.0 g, 345 mmol, 30.3 mL, 3.00 equivalent) was stirred at 80°C for 1 hour. TLC (petroleum ether / ethyl acetate = 5 / 1) showed that compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1) was consumed and new spots were formed. The reaction mixture was quenched at 15°C with H2O (200 mL) and extracted with 600 mL (200 mL x 3) of siRNA. The combined organic layer was concentrated under reduced pressure to obtain the residue. The residue was purified by column chromatography (SiO2, petroleum ether / ethyl acetate = 1 / 0 → 5 / 1) and further purified by washing with MTBE (methyl tert-butyl ether) (100 mL). Compound 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2) (10.6 g, 35.2 mmol, 30.6% yield, 99% purity) was obtained as a blue solid, and this was... 1 Confirmed by HNMR. 1 HNMR:(400MHz,DMSO-d6):δ 11.5(br d,J=0.9Hz,1H), 7.64~7.56(m,4H), 7.56~7.51(m,2H), 7.35(dd,J=1.8,2. 6Hz,1H), 7.30(t,J=7.8Hz,2H), 7.15~7.07(m,1H), 6.99(t,J=2.0Hz,1H).

[0104] Compound PLC-1.3: Step 1: A mixture of 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2) (1.0 g, 3.36 mmol), 2,4,6-trimethylbenzaldehyde (0.249 g, 1.68 mmol), and tosylic acid (50 mg) in 1,2-dichloroethane (80 mL) was heated at 50°C for 24 hours. LC-MS analysis showed that the desired product was present, with a major peak having m / e+=727.

[0105] Step 2: DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (454 mg, 2 mmol) was added to the mixture from Step 1 and stirred at room temperature for 1 hour. LC-MS analysis showed that the reaction was completed with one major peak with m / e- = 724.

[0106] Step 3: Triethylamine (0.85 mL, 6 mmol) and boron trifluoride diethyl etherate (BF3·OEt2) (1.1 mL, 9 mmol) were added to the mixture from Step 2 at 0°C. The whole mixture was heated at 50°C for 1 hour. The remaining triethylamine (0.5 mL) and BF3·OEt2 (0.5 mL) were added, and the mixture was heated at 50°C for another 1 hour. LCMS was performed, m / e - The reaction was completed at the main peak at =772. The mixture was diluted with 50 mL of dichloromethane (DCM), then washed twice with water and once with brine, then concentrated to 100 mL, loaded onto silica gel, and purified by flash chromatography using hexane / DCM (40% → 100% DCM) as the eluent. The desired main peak was collected, and after removing the solvent under reduced pressure, the desired product was obtained as a purple solid (1.06 g, 81.6% yield). Confirmed by LC-MS (APCI):C 42 H 31 Calculated value (M-) for BBr2F2N2: 770.1; Measured value: 770. 1 H NMR (400MHz, chloroform-d) δ 7.81~7.73(m,4H), 7.61~7.53(m,4H), 6.99~6.90(m,2H), 6.85(dd,J=8.3,6.9H z,4H), 6.78~6.71(m,4H), 6.42(s,2H), 6.00(s,2H), 1.98(s,6H), 1.85(s,3H).

[0107] Compound PLC-1.4: A mixture of compound PLC-1.3 (160 mg, 0.207 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (120 mg, 0.54 mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh3)4) (25 mg, 0.022 mol), and potassium carbonate (140 mg, 1.01 mmol) in 1,4-dioxane / water (8 mL / 1 mL) was degassed and then heated in a microwave reactor at 120 °C for 90 minutes. The resulting mixture was diluted in 20 mL of DCM, loaded onto silica gel, and purified by flash chromatography using DCM / ethyl acetate (0% → 20% ethyl acetate) as the eluent. The desired main peak was collected, and after removing the solvent under reduced pressure, the desired product was obtained as a dark solid (130 mg, 79% yield). 1 H NMR(400MHz,TCE-d2) δ 7.98~7.91(m,4H), 7.62~7.54(m,4H), 7.54~7.46(m,4H), 6.92~6.85(m,4H), 6.84(d,J=2.1Hz,2H), 6. 82~6.74(m,4H), 6.73~6.66(m,4H), 6.46(s,2H), 5.92(s,2H), 4.88(s,2H), 1.92(s,6H), 1.78(s,3H).

[0108] [ka]

[0109] Compound PLC-1.5: A mixture of 2-nitrophenol (6.6 g, 48 mmol) and KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes. Then copper powder (0.4 g) was added, followed by 100 mL of dimethylformamide anhydride (DMF). The mixture was stirred for 5 minutes, then 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The mixture was degassed and then heated under reflux for 1.5 hours. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture and allowed to stand for 2 hours. The precipitate was collected by filtration and dried overnight under vacuum to obtain a yellowish-brown solid (4.6 g). This was further purified by stirring in reflux acetic acid (50 mL) for 2 hours and then cooling to room temperature. After filtration and drying in air, a yellow solid (3.0 g, 41% yield) was obtained. Confirmed by LC-MS (APCI):C 18 H 10 Calculated value (M+H) for NO6: 336.0; Measured value: 336. 1 H NMR (400MHz, chloroform-d) δ 8.80(dd,J=8.5,1.2Hz,1H), 8.72(dd,J=7.3,1.2Hz,1H), 8.50(d,J=8.2Hz,1H), 8.19(dd,J=8.2,1.7Hz,1H), 7.90(dd,J=8. 5,7.3Hz,1H), 7.79(td,J=7.9,1.7Hz,1H), 7.54(td,J=8.0,1.3Hz,1H), 7.39(dd,J=8.3,1.2Hz,1H), 6.89(d,J=8.2Hz,1H).

[0110] Compound PLC-1.6: A mixture of 4-(2-nitrophenoxyl)-1,8-naphthalic anhydride (2.0 g, 6 mmol) and iron powder (less than 10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated under reflux for 30 minutes. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, completely dried in air, and then dried under vacuum to obtain a yellow solid (1.65 g, 90% yield). Confirmed by LC-MS (APCI): C 18 H 12 Calculated value (M+H) for NO4: 306.1; Measured value: 306.

[0111] Compound PLC-1.7:4-(2-aminophenoxy)-1,8-naphthalic anhydride (PLC-1.6) (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0°C. While stirring, pre-cooled hydrochloric acid (3 mL, 37 mmol) was added, and then sodium nitrite solution in 12 mL of water (3.29 g, 46 mmol) was added dropwise at 0°C. The mixture was stirred at 0°C for 1 hour, then transferred to an additional funnel, and refluxed copper sulfate solution (5.08 g, 20 mmol in 50 mL of water) was added dropwise over 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water and ethyl acetate, then dried in air and then under vacuum to obtain a yellow solid (0.92 g, 65% yield). Confirmed by LC-MS (APCI):C 18 Calculated value (M-) for H8O4: 288.0; Measured value: 288. 1 H NMR (400MHz, chloroform-d) δ 8.61(dd,J=17.1,8.1Hz,2H), 8.09(d,J=8.0Hz,1H), 7.97(d,J=7.9Hz,1H), 7.59(t,J=7.7Hz,1H), 7.40(t,J=8.1Hz,2H), 7.33(d,J=8.4Hz,1H).

[0112] Compound PLC-1.8: A mixture of 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (PLC-1.7) (100 mg, 0.347 mmol) and 4-(4-aminophenyl)butanoic acid (125 mg, 0.7 mmol) in 5 mL of DMF was heated in a microwave reactor at 165°C for 2.5 hours. 15 mL of acetone was added to this mixture, and the resulting precipitate was collected by filtration and dried in air to obtain a yellow solid (PLC-1.8) (120 mg, 77% yield). Confirmed by LC-MS (APCI): C 28 H 19 Calculated value (M-) for NO5: 449.1; Measured value: 449. 1H NMR(400MHz,DMSO-d6) δ 8.38(d,J=41.6Hz,4H), 7.81~6.97(m,8H), 2.69~2.64(m,2H), 2.26(t,J=7.2Hz,2H), 1.87(p,J=7.2Hz,2H).

[0113] Compound PLC-1: A mixture of compound PLC-1.4 (80 mg, 0.1 mmol), compound PLC-1.8 (100 mg, 0.222 mmol), 4-dimethylaminopyridinium / p-toluenesulfonate (DMAP / TsOH salt) (59 mg, 0.2 mmol), and N,N'-diisopropylcarbodiimide (DIC) (0.15 mL) in DCM was stirred overnight at room temperature, and then stirred at 45°C for 2 hours. The resulting mixture was loaded onto silica gel and purified by flash chromatography using dichloromethane (DCM) / ethyl acetate (0% → 10% ethyl acetate) as the eluent. The desired double-coupled product was collected as the second major peak. After removing the solvent, washing with methanol, and drying in air, the desired product was obtained as a dark solid (25 mg, 15% yield). Confirmation was made by 1H NMR. 1 H NMR(400MHz,TCE-d2) δ 8.49(dd,J=16.0,8.1Hz,4H), 7.99(d,J=8.2Hz,6H), 7.85(d,J=8.0Hz,2H), 7.63(dd, J=8.5,3.7Hz,8H), 7.50(t,J=7.8Hz,2H), 7.42~7.25(m,8H), 7.25~7.08(m,10H), 6.8 4(dt,J=36.5,7.3Hz,6H), 6.70(d,J=7.5Hz,4H), 6.48(s,2H), 5.93(s,2H), 2.80(t,J =7.7Hz,4H), 2.63(t,J=7.4Hz,4H), 2.11(t,J=7.7Hz,4H), 1.92(s,6H), 1.78(s,3H).

[0114] Synthesis of compound PLC-2 [ka]

[0115] Compound PLC-2.1:(4',4'''-(5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-3,7-diyl)bis([1,1'-biphenyl]-3-ol)): A 30 mL wide-neck microwave vial (Anton-Parr) was filled with a stirring bar, compound PLC-1.3 (0.300 mmol, 232 mg), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (0.800 mmol, 177 mg), K2CO3 (1.60 mmol, 221 mg), and Pd(PPh3)4 (0.030 mmol, 34.7 mg). Dioxane (8 mL) and water (1 mL) were added to a vial. The vial was sealed with a septum and argon was sprayed over it while stirring at room temperature for 5 minutes. The septum was replaced with a snap cap and septum, and the sample was irradiated in a microwave synthesizer at a target temperature of 120°C for 90 minutes. The crude reaction mixture was evaporated to dryness, dissolved in a small amount of DCM, and loaded onto approximately 60 mL of silica in a solid loader. The mixture was purified by silica gel flash chromatography (120 g, solid content, equilibrated with 100% hexane, 100% hexane (2 CV), 60% siRNA / hexane (30 CV) elution). The fraction containing the product was evaporated to dryness under vacuum to obtain a dark red solid, 173 mg (72% yield). 1 H NMR(400MHz,tetrachloroethane-d2) δ 8.05(d,J=8.5Hz,4H), 7.70(d,J=8.5Hz,4H), 7.35(t,J=7.8Hz,2H), 7.27(dt,J=7.9,1.2Hz,2H), 7.15(dd,J=2.5,1.6Hz,2H) , 7.00~6.93(m,2H), 6.91~6.83(m,6H), 6.82~6.76(m,4H), 6.56(s,2H), 6.02(s,2H), 4.94(s,2H), 2.00(s,6H), 1.87(s,3H). MS(APCI):Chemical formula C 54 H 41 Calculated value (M-) for BF2N2O2: 798; measured value: 798.

[0116] Compound PLC-2: ((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',3-diyl)bis(4-(4-(1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoyl A stirring bar, compound PLC-2.1 (0.015 mmol, 12.0 mg), 4-(4-(1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoic acid (PLC-1.8) (0.0375 mmol, 16.8 mg), and DMAP·pTsOH salt (0.0075 mmol, 2.2 mg) were placed in a 40 mL screw-cap vial. The vial was sealed with the screw cap under air and placed in a preheated aluminum heat block set to 70°C. After stirring the reaction mixture at 70°C for several minutes, N,N'-diisopropylcarbodiimide (DIC) (0.060 mmol, 0.0094 mL) was added. The vial was sealed with the screw cap and stirred at 70°C for 28 hours, then stirred at room temperature for the remainder of the weekend. TLC indicated that the reaction was not yet complete. The vial was reheated to 70°C, and 4-(4-(1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoic acid (PLC-1.8) (0.0221 mmol, 9.9 mg) and N,N'-diisopropylcarbodiimide (DIC) (0.060 mmol, 0.0094 mL) were added, followed by 4 mL of anhydrous THF (to improve the solubility of all reactants). The reaction mixture was stirred at 70°C for 90 minutes, at which point TLC indicated the completion of the reaction. The solvent was evaporated to dryness under vacuum, dissolved in a small amount of toluene, and loaded onto approximately 10 g of silica gel using a solid loader. The solution was purified by silica gel flash chromatography (80 g, solids, equilibrated with 100% toluene, 100% toluene (2 CV), followed by elution with 20% siRNA / toluene (30 CV)). After solvent removal, 22.0 mg of red solid (88% yield) was obtained. 1H NMR (400MHz, クロロホルム-d) δ 8.59(dd,J=13.1,8.1Hz,4H), 8.08~7.99(m,6H), 7.89(d,J=8.0Hz,2H), 7.68(d,J=8.5Hz,4H ), 7.57~7.49(m,4H), 7.49~7.31(m,12H), 7.30~7.22(m,6H), 7.09(ddd,J=8.0,2.4,1.1Hz,2 H), 6.98~6.91(m,2H), 6.86(t,J=7.6Hz,4H), 6.81~6.75(m,4H), 6.51(s,2H), 6.01(s,2H), 2 .85(t,J=7.6Hz,4H), 2.68(t,J=7.4Hz,4H), 2.17(p,J=7.6Hz,4H), 2.02(s,6H), 1.86(s,3H).

[0117] Compound PLC-3:

change

[0118] Compound PLC-3.1 (ethyl(2-(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-4-phenyl-1H-pyrrole-3-carboxylate): All ground glass joints were sealed with Teflon® tape. 250 mL 2N RBF was placed in an aluminum heat block and preheated to 90°C. An air condenser with a septum on top and a glass stopper on the second opening was fitted to the flask, and a stirring bar was inserted. The flask was flushed with argon through the top of the air condenser via a needle, and then zinc (granules, 10-20 mesh, 80.0 mmol, 5.231 g) was added. Anhydrous THF (20 mL) was added to the flask, followed by methanesulfonic acid (0.500 mmol, 0.0325 mL). After stirring the reaction mixture at 90°C for 5 minutes, 4'-(octyloxy)-[1,1'-biphenyl]-4-carbonitrile (15.0 mmol, 4.611 g) was added. A syringe pump was used. The mixture was set up, and benzyl 2-bromoacetate (22.5 mmol, 3.56 mL) was added dropwise over 1 hour with stirring at 90°C. The reaction mixture was heated at 90°C for 20 hours. The additional anhydrous THF (10 mL) was added (to replace the solvent lost by evaporation), and the reaction temperature was lowered to 85°C. Beta-nitrostyrene (10.0 mmol, 1.491 g) was added, followed immediately by iron trichloride (FeCl3) (6.00 mmol, 973 mg), and the reaction mixture was heated under argon at 85°C for 1 hour. The reaction mixture was confirmed to be complete by TLC. The reactants were removed from the heat, diluted with ethyl acetate (200 mL) and water (100 mL), and then sterilized to 6N The solution was acidified with HCl / aqueous solution (20 mL), and brine (50 mL) was added to break up the emulsion. The layers were separated. When the organic layer was washed with water (100 mL), another emulsion was obtained. This emulsion was broken up by adding 6N HCl and brine, as before. The organic layer was dried over MgSO4, filtered, and evaporated to dryness under vacuum. The crude product was evaporated onto 10:1 Celite:FlashSiO2 and purified by silica gel flash chromatography (330 g, solids, equilibrated with 10% DCM / hexane, 10% DCM / hexane (2 CV), 100% DCM (2 CV) elution).The fraction containing the product was evaporated to dryness under vacuum, yielding 1.409 g of a grayish-white solid in 25% yield. 1 1H NMR (400MHz, tetrachloroethane-d2) δ 8.52(d,J=2.5Hz,1H), 7.57(d,J=7.4Hz,6H), 7.48~7.43(m,2H), 7.39~7.28(m,3H), 7.26~7.17(m,3H), 7.02(d,J=8.8Hz,2H), 6.95~6.90(m,2) H), 6.87(d,J=2.6Hz,1H), 5.10(s,2H), 4.02(t,J=6.6Hz,2H), 1.82(p,J=6.8Hz,2H), 1.54~1.43(m,2H), 1.43~1.25(m,8H), 0.95~0.88(m,3H). MS(APCI):Chemical formula C 33 H 37 Calculated value for NO3 (M+H) = 496; measured value: 496.

[0119] Compound PLC-3.2: (2-hydroxyethyl 2-(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-4-phenyl-1H-pyrrole-3-carboxylate): A 100 mL two-necked round-bottom flask was placed in an aluminum heat block, fitted with a finned condenser, and a stirring bar was inserted. The heat block was preheated to 120°C. Compound PLC-3.1 (0.479 mmol, 267 mg) and sodium hydride (NaH) (9.575 mmol, 230 mg, 60% in mineral oil, 383 mg) were added to the flask. A septum and needle were fitted to the second neck to release pressure. Anhydrous ethylene glycol was carefully added to the flask while stirring at 120°C to release hydrogen gas. Once all hydrogen gas had been released, the septum was removed and replaced with a glass stopper. The reaction temperature was raised to 150°C, and the reaction mixture was stirred at this temperature for 1 hour. Since the reaction proceeded slowly (monitored by LC-MS), the stirring rate was increased to overcome the insolubility of the starting materials in ethylene glycol. The reactants were heated at 150°C for 3 hours with very vigorous stirring, and then heated overnight at room temperature. The reaction was completed in the morning. The reaction mixture was diluted with water (100 mL) and acidified with 6N HCl / aqueous solution (10 mL). After stirring at room temperature for 1 hour, the precipitate was filtered off and washed with water. The crude precipitate was dissolved in ethyl acetate and DCM and evaporated to dryness. The crude product was evaporated under vacuum on flash silica gel and purified by silica gel flash chromatography (120 g, equilibrated with 100% hexane, solids, 100% hexane (2 CV), 5% siRNA / hexane (0 CV) → eluted with 100% siRNA (30 CV)). The fraction containing the product was collected and evaporated to dryness under vacuum to obtain 127 mg of a grayish-white solid in 51% yield. 1H NMR (400MHz, Tactron-d2) δ 8.54(d,J=2.4Hz,1H), 7.66(s,4H), 7.59(d,J=8.7Hz,2H), 7.50~7.45(m,2H ), 7.44~7.39(m,2H), 7.38~7.32(m,1H), 7.01(d,J=8.8Hz,2H), 6.87(d,J=2 .5Hz,1H), 4.12~4.06(m,2H), 4.01(t,J=6.6Hz,2H), 3.55~3.47(m,2H), 1.8 1(p,J=6.7Hz,2H), 1.53~1.42(m,2H), 1.42~1.27(m,8H), 0.97~0.86(m,3H). MS(APCI):Chemical formula C 33 H 37 Calculated value of NO4についての(M+H)=512; Measured value: 512.

[0120] Compound PLC-3.3: (bis(2-hydroxyethyl)5,5-difluoro-10-mesityl-3,7-bis(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-2,8-dicarboxylate) (PLC-3.3): A stirring bar, compound PLC-3.2 (0.244 mmol, 125 mg), and mesitaldehyde (0.1283 mmol, 0.00189 mL) were added to a 40 mL screw-cap vial. The headspace was purged with argon, and the vial was then sealed with a screw-cap septum and placed in an aluminum heat block preheated to 75°C. Anhydrous DCE (5 mL) was added to the vial, and the solution was stirred for 10 minutes while being sprayed with nitrogen at 75°C. Then pTsOH (0.0.0366 mmol, 7.0 mg) was added together with anhydrous DCE (3 mL). Nitrogen spraying was continued for another 10 minutes at 75°C. The gas was switched to static argon, and the reaction mixture was stirred overnight under argon at 75°C. The next morning, additional mesitaldehyde (0.0339 mmol, 5.03 mg) was added, and the reaction mixture was stirred under argon at 75°C for another 30 minutes, at which point TLC did not show the starting materials. The reaction mixture was removed from the heat, DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (0.1586 mmol, 36 mg) was added, and the reaction mixture was stirred at room temperature for 1 minute. Then it was returned to the heat block and stirred at 75°C for 30 minutes to complete the oxidation. The reaction mixture was cooled to 0°C, and boron trifluoride diethyl etherate (BF3·OEt2) (1.098 mmol, 0.136 mL) and triethylamine (0.732 mmol, 0.102 mL) were rapidly and continuously added while stirring. After stirring the reaction mixture at 0°C for 1 minute, the addition of BF3·OEt2 (1.098 mmol, 0.136 mL) and triethylamine (0.732 mmol, 0.102 mL) was repeated. After stirring for another minute at 0°C, the reaction mixture was returned to the heat block and stirred at 75°C for 2 hours.BF3·OEt2 (1.464 mmol, 0.181 mL) and triethylamine (0.732 mmol, 0.102 mL) were further added at 75°C, and stirring was continued for 45 minutes. At this point, all dipyromethene was consumed by TLC. Flash silica gel (40 mL) was added to an Erlenmeyer flask, and the reaction mixture was diluted in this flask with DCM (approximately 100 mL). Methanol (25 mL) was added to quench the reaction mixture. The reaction mixture was evaporated to dryness under vacuum onto the silica gel. The crude reaction mixture was purified by silica gel flash chromatography (80 g, solid content, equilibrated with 100% hexane, eluted with 100% hexane (2 CV), 26% siRNA / hexane (19.7 CV), and 100% siRNA (15 CV)). The fraction containing the product was evaporated to dryness under vacuum, yielding 35 mg of a reddish-blue solid in 24% yield. MS (APCI): Chemical formula C. 76 H 81 Calculated value (M-) for BF2N2O8: 1199; measured value: 1199.

[0121] Compound PLC-3 (bis(2-((4-(4-(1,3-dioxo-3,6-dihydroanthra[2,1,9-def]isoquinoline-2(1H)-yl)phenyl)butanoyl)oxy)ethyl)5,5-difluoro-10-mesityl-3,7-bis(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-2,8-dicarboxylate): A 40 mL screw-cap vial was placed in an aluminum heat block and a stirring bar was inserted. PLC-3.3 (0.0146 mmol, 17.5 mg), 4-(4-(1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoic acid (0.0438 mmol, 19.6 mg) (PLC-1.8), and DMAP·pTsOH salt (0.0073 mmol, 2.1 mg) were added to the vial. Anhydrous DCM (4 mL) was added to the vial. The vial was sealed with a PTFE-lined screw cap and sonicated for approximately 30 seconds. N,N'-diisopropylcarbodiimide (DIC) (0.073 mmol, 0.0114 mL) was added while stirring at room temperature. The sealed vial was stirred in air at room temperature for 5 minutes, then the heat block was set to 45°C and the reaction mixture was stirred at this temperature overnight. In the morning, DCM was evaporated under a nitrogen stream, and the solvent was replaced with anhydrous dichloroethane (DCE) (4 mL). The heat block temperature was raised to 70°C, and the reaction mixture was stirred at this temperature for 1 hour to complete the reaction. The crude reaction mixture was loaded into a cartridge packed with 60 mL of flash silica gel and purified by silica gel flash chromatography (80 g, equilibrated with 100% hexane, eluted with 100% hexane (2 CV) and 70% siRNA / hexane (40 CV)). The fraction containing the product was evaporated to dryness under vacuum to obtain 15.3 mg of dark solid (57.3% yield). 1H NMR (400MHz, chloroform-d) δ 8.61(dd,J=16.2,8.1Hz,4H), 8.07(dd,J=8.1,1.5Hz,2H), 7.94(d,J=8.0Hz,2H), 7.68(d,J=8.1Hz,4H), 7.60~7.50(m, 10H), 7.40~7.33(m,4H), 7.29(d,J=8.3Hz,6H), 7.21(d,J=8.3Hz,4H), 6.97~6.88(m,6H), 6.86~6.76(m,8H), 5.95(s,2H) ), 3.96(t,J=6.6Hz,4H), 3.94~3.88(m,4H), 3.64~3.58(m,4H), 2.63(t,J=7.6Hz,4H), 2.20(t,J=7.4Hz,4H), 2.00(s,6H) ), 1.88(p,J=7.6Hz,4H), 1.82(s,3H), 1.80~1.73(m,4H), 1.45(p,J=6.7Hz,4H), 1.38~1.19(m,16H), 0.92~0.84(m,6H).

[0122] Synthesis of compound PLC-4: [ka]

[0123] Compound PLC-4.1: Bromine (1.98 g, 12 mmol) was added to a mixture of PLC-1.7 (290 mg, 1.0 mmol) in ortho-dichlorobenzene (30 mL). The mixture was heated at 75°C for 30 hours. After cooling to room temperature, the solid was collected by filtration and dried in air to obtain 290 mg of the desired product, a yellow solid. The filtrate was loaded onto silica gel and purified by flash chromatography using hexane / dichloromethane (50% → 100% dichloromethane) as the eluent. The desired fraction was collected, and the solvent was removed to obtain 110 mg of a yellow solid. A total of 400 mg of product was obtained in 89.7% yield. LCMS(APCI-):C 18 Calculated value (M-) for H6Br2O4: 443.9; Measured value: 444. 11H NMR (400 MHz, d2-TCE) δ 9.40 (dd, J = 8.5, 1.5 Hz, 1H), 8.71 (s, 1H), 8.67 (s, 1H), 7.60 (ddd, J = 8.4, 7.1, 1.5 Hz, 1H), 7.48 (dd, J = 8.3, 1.4 Hz, 1H), 7.38 (ddd, J = 8.5, 7.1, 1.4 Hz, 1H).

[0124] Compound PLC-4.2: A mixture of PLC-4.1 (190 mg, 0.426 mmol), 4-(4-aminophenyl)butanoic acid (180 mg, 0.64 mmol), and 4-(N,N-dimethylamino)pyridine (4 mg) in anhydrous N,N-dimethylformamide (DMF) (4 mL) was heated at 165 °C for 2.5 h. After cooling to room temperature and standing overnight, the solid was collected by filtration, washed with acetone, and dried in a vacuum oven at 90 °C for 1 h to give a yellow solid (220 mg, 84.5% yield). LCMS (APCI-): C 28 H 17 Calculated for CBr2NO5 (M-): 604.95; found: 605. 1 1H NMR (400 MHz, DMSO-d6) δ 9.42 (dd, J = 8.6, 1.5 Hz, 1H), ⑧.57 (d, J = 4.6 Hz, 2H), 7.83 - 7.68 (m, 1H), 7.63 - 7.44 (m, 2H), 7.34 (d, J = 8.3 Hz, 2H), 7.31 - 7.16 (m, 2H), 2.67 (dd, J = 4.8, 2.8 Hz, 2H), 2.28 (t, J = 7.4 Hz, 2H), 1.95 - 1.80 (m, 2H).

[0125] Compound PLC-4.3: A mixture of compound PLC-4.2 (100 mg, 0.165 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (170 mg, 0.66 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (Pd(dppf)Cl2) (20 mg, 0.027 mmol), and potassium carbonate (138 mg, 1 mmol) in THF / water (5 mL / 0.5 mL) was degassed and then heated at 80 °C for 2 h. After cooling to room temperature, the precipitate was collected by filtration, washed with acetone, and then dried in a vacuum oven at 90 °C for 2 h. A yellow solid (142 mg, 94% yield) was obtained. LCMS(APCI-): C 44 H 23 F 12 Calculated for C 1 H

[0126] Compound PLC-4: A mixture of compound PLC-1.4 (20 mg, 0.025 mmol), PLC-4.3 (55 mg, 0.0626 mmol), 4-dimethylaminopyridinium / p-toluenesulfonate (DMAP / TsOH salt) (30 mg, 0.1 mmol), and N,N'-diisopropylcarbodiimide (DIC) (0.1 mL) in 5 mL of DCM was stirred at room temperature for 60 h. The mixture was loaded onto silica gel and purified by flash chromatography using a eluent of dichloromethane / ethyl acetate (0%→5% ethyl acetate). The desired fractions were collected and concentrated under reduced pressure. The resulting solid was washed with methanol and dried in air to give the desired product as a dark green solid (18 mg, 29% yield). 11H NMR (400 MHz, d2-TCE) δ 8.64 (s, 2H), 8.40 (s, 2H), 8.16 (s, 4H), 8.05 - 7.88 (m, 12H), 7.63 (dd, J = 8.6, 2.9 Hz, 8H), 7.44 - 7.32 (m, 6H), 7.27 - 7.08 (m, 10H), 6.96 - 6.83 (m, 6H), 6.79 (t, J = 7.6 Hz, 4H), 6.70 (d, J = 7.4 Hz, 4H), 6.47 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 7.6 Hz, 4H), 2.62 (t, J = 7.2 Hz, 4H), 2.17 - 2.03 (m, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

[0127] Synthesis of the compound: PLC-5: [Chemical formula]

[0128] Compound PLC-5: A mixture of PLC-2.1 (20 mg, 0.025 mmol), PLC-4.3 (61 mg, 0.07 mmol), 4-dimethylaminopyridinium / p-toluenesulfonate (DMAP / TsOH salt) (20 mg, 0.068 mmol), and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC·HCl) (134 mg, 0.7 mmol) was stirred in 5 mL of dichloromethane at 40 °C overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using a hexane / ethyl acetate (0% → 20% ethyl acetate) eluent. The desired fractions were collected and concentrated under reduced pressure. The resulting solid was washed with methanol and dried in air to obtain the desired product as a dark green solid (20 mg, 32% yield). 1H NMR(400MHz,d2-TCE) δ 8.64(s,2H), 8.39(s,2H), 8.16(d,J=1.6Hz,4H), 8.04~7.87(m,12H), 7.64(d,J=8.3Hz, 4H), 7.49(s,2H), 7.45~7.28(m,10H), 7.19(dd,J=17.8,8.1Hz,6H), 7.04(s,2H), 6.95~ 6.83(m,6H), 6.78(t,J=7.4Hz,4H), 6.69(d,J=7.3Hz,4H), 6.47(s,2H), 5.94(s,2H), 2. 80(t,J=7.8Hz,4H), 2.63(t,J=7.4Hz,4H), 2.16~2.02(m,4H), 1.91(s,6H), 1.78(s,3H).

[0129] Synthesis of compound PLC-6: [ka]

[0130] A mixture of compound PLC-6.1:4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol) and 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 minutes, then anhydrous NMP (50 mL) was added, followed by sodium hydroxide (0.2 g, 5 mmol) and copper powder (0.318 g, 5 mmol). The mixture was sprayed with argon for 20 minutes, and then heated overnight at 180°C under an argon atmosphere. After cooling to room temperature, 50 mL of 20% hydrochloric acid aqueous solution was added dropwise to the solution, followed by 50 mL of water. The resulting mixture was left to stand for 3 hours, then filtered to collect the precipitate, which was dried under vacuum to obtain 4.6 g of crude product. The crude product was dispersed in 30 mL of acetone and stirred overnight at room temperature to dissolve impurities. The mixture was filtered and dried under vacuum to obtain a yellowish-brown solid (3.3 g, 80% yield) as the desired product. LC-MS(APCI+):C 18 Calculated value (M+H) for H9BrNO6: 413.95; Measured value: 414. 11H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 - 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H).

[0131] Compound PLC-6.2: A mixture of compound PLC-6.1 (1.5 g, 3.6 mmol) and iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125 °C for 30 minutes. After cooling to room temperature, 100 mL of water was added to the mixture with stirring. The resulting mixture was filtered, washed with water, and dried in air and then in vacuo to give a solid (1.35 g, 82% yield). LCMS (APCI-): C 18 H 10 Calculated for C H BrNO4 = 382.98; Found: 383. 1 1H NMR (400 MHz, DMSO-d6) δ 9.01 - 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H).

[0132] Compound PLC-6.3: Compound PLC-6.2 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL) / water (10 mL) and cooled to 0 °C. While stirring, pre-cooled hydrochloric acid (2.8 mL, 34.5 mmol) was added, and then a sodium nitrite solution (3.57 g, 52 mmol) in 15 mL of water was added dropwise at 0 °C. After stirring the whole at 0 °C for 1 hour, it was transferred to an addition funnel and added dropwise to a copper sulfate solution (12 g, 47 mmol, 140 mL of water) at 130 °C over 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water (100 mL × 3), then stirred in 50 mL of acetone at 40 °C for 30 minutes, filtered, and dried in air and then in vacuo to give a yellowish-brown solid (1.76 g, 70% yield). LCMS (APCI+): C 18 Calculated for C H8BrO4 (M + H) = 366.95; Found: 367. 1H NMR(400MHz,d2-TCE) δ 8.51(dd,J=12.3,8.1Hz,2H), 8.12(d,J=2.3Hz,1H), 7.86(d,J=7.9Hz,1H), 7.60(dd,J=8.8,2.3Hz,1H), 7.28(d,J=8.3Hz,1H), 7.23(d,J=8.8Hz,1H).

[0133] Compound PLC-6.4: A mixture of compound PLC-6.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol), and DMAP (12.2 mg, 0.1 mmol) in 10 mL of DMF was heated in a microwave reactor at 165°C for 2.5 hours. The resulting solution was added dropwise to 50 mL of acetone with stirring. A precipitate formed, which was filtered and dried overnight in a vacuum oven at 60°C to obtain the desired product as a yellowish-brown solid (0.49 g, 62% yield). LCMS(APCI-):C 28 H 18 Calculated value for BrNO5 = 527.04; Measured value: 527. 1 H NMR(400MHz,DMSO-d6) δ 8.54(d,J=2.3Hz,1H), 8.41(dd,J=9.9,8.0Hz,2H), 8.33(d,J=7.9Hz,1H), 7.71(dd,J=8.8,2.3Hz,1H), 7.39(dd,J=8. 6,4.2Hz,2H), 7.25(d,J=8.0Hz,2H), 7.17(d,J=7.9Hz,2H), 2.63~2.55(m,2H), 2.27~2.15(m,2H), 1.87~1.73(m,2H).

[0134] Compound PLC-6.4 (385 mg, 0.729 mmol), 3,5-bis-(trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol), Pd(dppf)Cl2 (36 mg, 0.05 mmol), and potassium carbonate (276 mg, 2 mmol) were degassed in a cosolvent of compound PLC-6.5: THF / DMF / water (20 mL / 4 mL / 2 mL) and then heated overnight at 80°C. The mixture was post-treated with 200 mL of ethyl acetate and 50 mL of 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected, washed with brine (100 mL x 2), dried over sodium sulfate, and then dry-loaded onto silica gel. It was purified by flash chromatography using DCM / EA (0% → 40% EA containing 0.1% TFA) as the eluent. The main desired fraction was collected, and the solvent was removed under reduced pressure to obtain a yellow solid (340 mg, 70.5% yield). LC-MS(APCI-):C 36 H 21 Calculated value for F6NO5 = 661.13; measured value: 661. 1 H NMR(400MHz,d2-TCE) δ 8.57(dd,J=19.2,8.1Hz,2H), 8.18(d,J=2.2Hz,1H), 8.05(d,J=8.0Hz,1H), 8.03~7.98(m,2H), 7.87(s,1H), 7.72(dd,J=8.6,2.2Hz,1 H), 7.48(d,J=8.6Hz,1H), 7.33(d,J=8.3Hz,3H), 7.21~7.12(m,2H), 2.72(t,J=7.6Hz,2H), 2.39(t,J=7.3Hz,2H), 2.04~1.97(m,2H).

[0135] Compound PLC-6: A mixture of compound PLC-1.4 (20 mg, 0.025 mmol), compound PLC-6.5 (52.9 mg, 0.08 mmol), DMAP / TsOH salt (20 mg, 0.068 mmol), and EDC·HCl (110 mg, 0.57 mmol) in DCM was stirred overnight at room temperature. The resulting mixture was loaded onto silica gel and purified by flash chromatography using DCM / ethyl acetate (0% → 10% ethyl acetate) as the eluent. The desired red fraction was collected. After removing the solvent, the solid was washed with methanol and dried in air to obtain the desired product as a dark solid (34 mg, 65% yield). 1 Confirmed by 1H NMR (400MHz, methylene chloride-d2): δ 8.64 (d, J=7.8Hz, 2H), 8.57 (d, J=8.3Hz, 2H), 8.28 (d, J=2.2Hz, 2H), 8.17 (s, 4H), 8.11~7.96 (m, 8H), 7.83 (dd, J=8.6, 2.2Hz, 2H), 7.78~7.70 (m, 8H), 7.55 (d, J=8.6Hz, 2H), 7.52~7.45 (m, 4H), 7.37~7.28 (m, 6H) , 7.27~7.20(m,4H), 7.05~6.97(m,2H), 6.92(dd,J=8.4,6.7Hz,4H), 6.88~6.81(m,4H), 6.58(s,2H), 6.0 8(s,2H), 2.92(t,J=7.7Hz,4H), 2.75(t,J=7.4Hz,4H), 2.23(p,J=7.6Hz,4H), 2.06(s,6H), 1.91(s,3H).

[0136] Synthesis of compound PLC-7: [ka]

[0137] Compound PLC-7.1: A mixture of PLC-1.7 (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione) (100 mg, 0.347 mmol) and 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) in DMF was heated in a microwave reactor at 165°C for 2 hours. After cooling to 50°C, 1.5 mL of acetone was added dropwise to the resulting solution to form a yellow precipitate, which was collected by filtration, washed with acetone, and dried in air to obtain a yellow solid (88 mg, 61% yield). Confirmed by LC-MS (APCI):C 26 H 15 Calculated value (M-) for NO5: 421.1; Measured value: 421. 1 H NMR (400MHz, DMSO-d6) δ 8.27 (d, J=45.1Hz, 4H), 7.67~7.00 (m, 8H), 3.58 (s, 2H).

[0138] Compound PLC-7: A mixture of compound PLC-1.4 (40 mg, 0.05 mmol), compound PLC-7.1 (67 mg, 0.16 mmol), DMAP / TsOH salt (20 mg, 0.068 mmol), and EDC·HCl (110 mg, 0.57 mmol) in 10 mL of DCM was stirred overnight at room temperature, and then heated overnight at 40°C. The resulting mixture was loaded onto silica gel and purified by flash chromatography using DCM / ethyl acetate (0% → 10% ethyl acetate) as the eluent. The desired red fraction was collected. After removing the solvent, the solid was triturated with methanol and dried in air to obtain the desired product as a dark solid (38 mg, 47% yield). 1Confirmed by H NMR (400MHz,d2-TCE) δ 8.46(dd,J=19.0,8.1Hz,4H), 7.99(d,J=8.3Hz,6H), 7.81(d,J=8.2Hz,2H), 7.67 ~7.60(m,8H), 7.56(d,J=8.2Hz,4H), 7.51(t,J=7.7Hz,2H), 7.35~7.26(m,8H), 7 .18(dd,J=8.5,2.0Hz,6H), 6.87(d,J=7.6Hz,2H), 6.79(t,J=7.5Hz,4H), 6.71(d ,J=7.3Hz,4H), 6.48(s,2H), 5.93(s,2H), 3.95(s,4H), 1.92(s,6H), 1.78(s,3H).

[0139] Synthesis of compound PLC-8: [ka]

[0140] Compound PLC-8.1: A mixture of compound PLC-6.4 (649 mg, 1.23 mmol), 4-(trifluoromethyl)phenylboronic acid (467 mg, 2.46 mmol), Pd(dppf)Cl2 (45 mg, 0.06 mmol), and potassium carbonate (345 mg, 2.5 mmol) in a cosolvent of THF / DMF / water (30 mL / 6 mL / 3 mL) was degassed and then heated overnight at 80°C. The mixture was post-treated with 300 mL of ethyl acetate and 50 mL of 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (150 mL x 3). The organic phase was collected, washed with brine (100 mL x 2), dried over sodium sulfate, and then dry-loaded onto silica gel. It was purified by flash chromatography using DCM / EA (0% → 80% EA containing 0.1% TFA) as the eluent. The main desired fraction was collected, and the solvent was removed under reduced pressure to obtain a yellow solid (414 mg, 57% yield). 11H NMR (400 MHz, d2-TCE) δ 8.55 (dd, J = 18.1, 8.1 Hz, 2H), 8.16 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.68 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 - 7.59 (m, 2H), 7.43 (d, J = 8.6 Hz, 1H), 7.32 (tt, J = 8.2, 4.2 Hz, 5H), 7.20 - 7.13 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.4 Hz, 2H).

[0141] Compound PLC-8: A mixture of compound PLC-1.4 (26 mg, 0.0326 mmol), compound PLC-8.1 (59 mg, 0.1 mmol), DMAP / TsOH salt (15 mg, 0.051 mmol), and EDC·HCl (60 mg, 0.31 mmol) in 5 mL of DCM was stirred at room temperature overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM / ethyl acetate (0% → 10% ethyl acetate). The desired red fraction was collected. After removing the solvent, the solid was washed with methanol and dried in air to obtain the desired product as a dark solid (46 mg, 72% yield). 1 1H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 18.1, 8.1 Hz, 4H), 8.11 (d, J = 2.2 Hz, 2H), 7.97 (dd, J = 17.1, 8.2 Hz, 6H), 7.71 - 7.56 (m, 14H), 7.39 (dd, J = 10.8, 8.4 Hz, 6H), 7.27 (dd, J = 13.0, 8.3 Hz, 6H), 7.23 - 7.17 (m, 4H), 7.17 - 7.10 (m, 4H), 6.94 - 6.84 (m, 2H), 6.79 (t, J = 7.5 Hz, 4H), 6.70 (d, J = 7.1 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 7.5 Hz, 4H), 2.63 (t, J = 7.3 Hz, 4H), 2.12 (q, J = 7.6 Hz, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

[0142] Synthesis of compound PLC-9:

Chemical Structure

[0143] Compound PLC-9.1: 2-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)acetic acid. Compound PLC-6.3 (6.3 g, 17.159 mmol, 1 equivalent) was suspended in 35 mL of anhydrous DMSO, and glycine (2.31 g, 30.77 mmol, 1.8 equivalents) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 130 °C for 1 hour (the mixture did not dissolve), then heated to 160 °C for 1 hour, and LMCMS indicated that the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL), and then dried in a vacuum oven to obtain 6.5 g of a greenish-yellow solid (90% yield). MS(APCI): Chemical formula C 20 H 10 Calculated value (M-) for BrNO5: 424; Measured value: 424. 1 H NMR(400MHz,DMSO-d6) δ 8.65(s,1H), 8.50(s,1H), 8.46(d,J=8.2Hz,2H), 8.09(d,J=8.0Hz,2H), 7.9 9(d,J=8.7Hz,1H), 7.87(d,J=8.0Hz,2H), 7.58(d,J=8.6Hz,1H), 7.45(d,J= 8.4Hz, 1H), 4.71(s, 2H).

[0144] Compound PLC-9.2, 2-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)acetic acid (compound PLC-9.1) (4.24 g, 10.0 mmol, 1 equivalent), was suspended in 2-methyl-THF (150 ml) and H2O (5.0 ml). 4-(tert-butyl)phenylboronic acid (3.56 g, 20 mmol, 2 equivalents), K2CO3 (2.76 g, 20 mmol, 2 equivalents), and Pd(dppf)Cl2·DCM (163.3 mg, 0.2 mmol, 0.02 equivalents) were added. The reaction mixture was degassed three times using a Vac-Fill argon cycle and heated and stirred at 95°C for 12 hours under an argon atmosphere. After cooling to room temperature, ethyl acetate (150 ml) acidified to pH 4-5 with 1N HCl was added. The organic layer was washed with water, separated, and concentrated. The residue was stirred in DMF (15 ml), filtered to obtain a solid, washed with MeOH (50 mL), and then dried in a vacuum oven to obtain 4.1 g of a greenish-yellow solid product (85% yield). MS(APCI): Chemical formula C 30 H 23 Calculated value (M-) for NO5: 477; Measured value: 477. 1 H NMR(400MHz,DMSO-d6) δ 8.33(d,J=6.1Hz,3H), 8.24(d,J=7.9Hz,1H), 7.95(s,1H), 7.78(d,J=8.3Hz,1H), 7.70(d,J=7.9Hz,2H), 7.50(d,J=7.9Hz,2 H), 7.39(d,J=8.3Hz,1H), 7.29(d,J=8.2Hz,1H), 4.52(s,2H), 2.89(s,3H), 2.73(s,3H), 2.54~2.47(m,21H), 1.34(s,10H).

[0145] Compound PLC-9:(5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4λ 4 ,5λ 4-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)acetate): Compound PLC-9.2 (143.25 mg, 0.30 mmol, 3 equivalents) was suspended in anhydrous DCM (10.0 ml) and PLC-1 0.4 (39.93 mg, 0.05 mmol, 1 equivalent), DMAP-pTSA (58.8 mg, 0.2 mmol, 4 equivalents), and EDC·HCl (47.92 mg, 0.25 mmol, 5 equivalents) were added, and the mixture was stirred at room temperature under an argon atmosphere for 5 hours. The mixture was diluted with DCM (150 ml), filtered, and the solid was washed with 50 ml of DCM. The filtrate was collected and loaded onto an 80 g SiO2 column. Elution was performed with Hex-DCM (1 / 1), DCM alone, and then with 0.5% EA in DCM. The good fractions were concentrated and then washed with MeOH to obtain a yield of 79 mg, 91%. 1 H NMR(400MHz,) δ 8.62(d,J=7.9Hz,2H), 8.56(d,J=8.4Hz,2H), 8.19(d,J=2.1Hz,2H), 8.04~7.97(m,3H), 7.95(s,4H), 7.71(dd,J=8.6,2.1Hz,2H), 7.61(dd,J=8.6,1.9Hz,8H), 7.57~7.53(m,4H), 7.45(d,J=8.5Hz,4H), 7 .40(d,J=8.6Hz,2H), 7.29(d,J=8.3Hz,2H), 7.20(d,J=8.6Hz,5H), 6.86(d,J=7.5Hz,3H), 6.78(t,J= 7.5Hz,4H), 6.69(d,J=7.2Hz,4H), 6.46(s,2H), 5.14(s,5H), 1.91(s,7H), 1.77(s,4H), 1.31(s,18H).

[0146] Synthesis of compound PLC-10: [ka]

[0147] Compound PLC-10.1: 2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)acetic acid. Compound PLC-9.1 (7.0 g, 16.50 mmol, 1 equivalent) was suspended in 2-methyl THF (150 mL), and 4-(trifluoromethyl)benzeneboronic acid (5.648 g, 29.7 mmol, 1.8 equivalents), K2CO3 (4.65 g, 33 mmol, 2 equivalents), H2O (15 mL), and Pd(dppf)Cl2·DCM (269.5 mg, 0.33 mmol, 0.02 equivalents) were added. The mixture was subjected to three Vac-Fill Argon cycles, stirred, heated at 95°C under an argon atmosphere for 12 hours, cooled to room temperature, stirred with 1N HCl (20 mL) for 15 minutes, and then held at room temperature for 1 hour. The solid was filtered, stirred with DMF at room temperature for 15 minutes, then filtered again, washed with MeOH, and then dried in a vacuum oven to obtain 6.70 g of a greenish-yellow solid, which was used in the next step without further purification (83% yield). MS(APCI): Chemical formula C 27 H 14 Calculated value (M-) for FNO5: 489; Measured value: 489. 1 H NMR(400MHz,DMSO-d6) δ 8.52(s,1H), 8.37(q,J=8.1,7.7Hz,3H), 8.04(d,J=7.9Hz,2H), 7.93(d,J=8.7Hz,1H ), 7.84(d,J=8.0Hz,2H), 7.49(d,J=8.6Hz,1H), 7.34(d,J=8.3Hz,1H), 4.67(s,2H).

[0148] Compound PLC-10:(5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4λ 4 ,5λ 4-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)acetate). Compound PLC-10.1 (73.4 mg, 0.15 mmol, 3 equivalents) was suspended in anhydrous DCM (10.0 ml), compound PLC-1.4 (39.93 mg, 0.05 mmol, 1 equivalent), DMAP-pTSA (58.8 mg, 0.2 mmol, 4 equivalents), and EDC·HCl (47.92 mg, 0.25 mmol, 5 equivalents) were added, and the mixture was stirred at room temperature under an argon atmosphere for 5 hours. The mixture was diluted with DCM (150 ml), filtered, and the solid was washed with 50 ml of DCM. The filtrate was collected and loaded onto an 80 g SiO2 column. Elution was performed with Hex-DCM (1 / 1), DCM alone, then 0.5% EA with DCM, followed by washing with MeOH to obtain a yield of 82 mg, 94%. 1 H NMR(400MHz) δ 8.63(d,J=7.9Hz,1H), 8.58(d,J=8.3Hz,1H), 8.19(d,J=2.1Hz,1H), 8.01(d,J=8.2Hz,1H), 7.96(d, J=8.3Hz,2H), 7.71(d,J=2.5Hz,4H), 7.61(d,J=8.1Hz,3H), 7.45(d,J=8.6Hz,1H), 7.32(d,J=8.4Hz ,1H), 7.20(d,J=8.6Hz,2H), 6.87(t,J=7.3Hz,1H), 6.78(t,J=7.6Hz,2H), 6.69(d,J=7.5Hz,2H),6. 45(s,2H), 5.24(s,1H), 5.14(s,2H), 1.96(s,1H), 1.91(s,3H), 1.77(s,2H), 1.18(d,J=6.5Hz,6H).

[0149] Synthesis of compound PLC-11: [ka]

[0150] Compound PLC-11.1:(3,7-bis(4-bromophenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine): A 250 mL 2N round-bottom flask was placed in an aluminum heat block and a stirring bar was inserted. A finned condenser / gas adapter and a flow control valve were attached to the flask. The system was flushed with argon. 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (3.00 mmol, 895 mg) and 2,6-dichlorobenzaldehyde (1.530 mmol, 268 mg) were added to the flask, followed by anhydrous dichloroethane (40 mL). Under an argon atmosphere, nitrogen was sprayed onto the reaction mixture for 2 minutes, then pTsOH·H2O (0.450 mmol, 86 mg) was added, followed by an additional 10 mL of anhydrous dichloroethane. TLC showed spot-to-spot conversion to the desired dipyrrolomethane at room temperature for 15 minutes. Nitrogen spraying was discontinued, and the reaction mixture was stirred under argon. The reaction mixture was stirred under argon overnight. The next day, DDQ (1.80 mmol, 409 mg) was added, followed by anhydrous dichloroethane, and the reaction mixture was stirred at room temperature for 1 hour. Et3N (13.5 mmol, 1.7 mL) and BF3·OEt2 (9.00 mmol, 1.3 mL) were added to the reaction mixture, and the reaction mixture was stirred at room temperature for 2 minutes. The addition of Et3N (13.5 mmol, 1.7 mL) and BF3·OEt2 (9.00 mmol, 1.3 mL) was repeated, and the reaction mixture was stirred at room temperature for 1 hour. The heat block was set to 80°C, and the reaction mixture was stirred at this temperature for 1 hour. The reaction mixture was cooled to room temperature, diluted with 300 mL of ethyl acetate, and quenched with methanol (25 mL). The reaction mixture was extracted with saturated NaHCO3 aqueous solution (3 × 100 mL) and brine (50 mL), dried over MgSO4, filtered, and evaporated to dryness under vacuum. The crude product was dissolved in DCM and evaporated under vacuum onto approximately 40 mL of flash silica gel. The product was purified by silica gel flash chromatography (220 g, solids, equilibrated 50% toluene / hexane, eluted 50% toluene / hexane (2 CV) → 75% toluene / hexane (30 CV)). The fraction containing the product was evaporated to dryness under vacuum.748 mg of a dark pink solid was obtained in a 62% yield (based on pyrrole). MS(APCI): Chemical formula C. 39 H 23 Calculated value (M-) for BBr2Cl2F2N2: 796; measured value: 796. 1 ¹H NMR (400MHz, tetrachloroethane-d2) δ 7.87~7.79 (m,4H), 7.66~7.59 (m,4H), 7.03~6.90 (m,10H), 6.57~6.44 (m,5H).

[0151] Compound PLC-11.2:(4',4'''-(10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4-ol)):PLC-11.2 was synthesized from PLC-11.1 (0.650 mmol, 519 mg), (4-hydroxyphenyl)boronic acid (3.90 mmol, 538 mg), K2CO3 (15.02 mmol, 2.075 g), and Pd(dppf)Cl2 (0.065 mmol, 48 mg) in anhydrous THF (100 mL) and water (10 mL), in the same manner as described above. The crude reaction mixture was quenched with acetic acid (10 mL) and flash silica gel (approximately 40 mL) was added. The crude reaction mixture was evaporated to dryness under vacuum. The mixture was purified by silica gel flash chromatography (120 g, equilibrated with 100% hexane, eluted with 100% hexane (2 CV) → 100% alkylammonium sulfate (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A dark solid, 501 mg (93% yield), was obtained. MS (APCI): Chemical formula C 51 H 33 Calculated value (M-) for BCl2F2N2O2: 824; measured value: 824. 1 ¹H NMR (400MHz, tetrachloroethane-d2) δ 8.10~8.01 (m,4H), 7.73~7.64 (m,4H), 7.63~7.54 (m,4H), 7.08~6.89 (m,14H), 6.62~6.45 (m,5H).

[0152] Compound PLC-11:((10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(1,3-dioxo-1H-xantheno[2,1,9-def Isoquinoline-2(3H)-yl(phenyl)butanoate)):PLC-11 was synthesized from PLC-11.2 (0.100 mmol, 83 mg), PLC-1.8 (0.300 mmol, 135 mg), DMAP·pTsOH salt (0.400 mmol, 118 mg), and EDC·HCl (0.250 mmol, 48 mg) in anhydrous HCl (5 mL). The complete reaction was obtained by repeating the addition of EDC·HCl (0.250 mmol, 48 mg). The reaction mixture was evaporated to dryness under vacuum, dissolved in DCM, loaded onto flash silica gel (approximately 40 mL in a solid loader), and purified by silica gel flash chromatography (120 g, equilibrated 100% DCM, eluted 100% DCM (2 CV) → 10% Â / DCM (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. 116 mg (69% yield) was obtained. MS (APCI): Chemical formula C 107 H 67 BCl2F2N4O 10 The calculated value (M-) for this is 1686; the measured value is 1686. 1 1H NMR (400MHz, methylene chloride-d2) δ 8.65(d,J=7.9Hz,2H), 8.60(d,J=8.3Hz,2H), 8.22(s,4H), 8.14(dd,J=8.0, 1.6Hz,2H), 8.02(d,J=8.0Hz,2H), 7.74~7.67(m,4H), 7.63~7.54(m,6H), 7. 50(s,4H), 7.46~7.30(m,18H), 7.29~7.24(m,4H), 7.20~7.13(m,4H), 7.06~ 7.00(m,8H), 4.04(s,4H), 2.76(hept,J=7.0Hz,4H), 1.16(d,J=6.8Hz,24H).

[0153] Synthesis of compound PLC-12: [ka]

[0154] Compound PLC-12.1: A mixture of 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (compound PLC-1.7) (100 mg, 0.347 mmol) and 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) in 5 mL of DMF was heated in a microwave reactor at 165°C for 2 hours. After cooling to 50°C, 1.5 mL of acetone was added dropwise to the resulting solution to form a yellow precipitate, which was collected by filtration, washed with acetone, and dried in air to obtain a yellow solid (88 mg, 61% yield). Confirmed by LC-MS (APCI):C 26 H 15 Calculated value (M-) for NO5: 421.1; Measured value: 421. 1 H NMR (400MHz, DMSO-d6) δ 8.27 (d, J=45.1Hz, 4H), 7.67~7.00 (m, 8H), 3.58 (s, 2H).

[0155] Compound PLC-12((10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl PLC-12 (acetate) was synthesized from PLC-12.1 (0.020 mmol, 16.5 mg), 2-(4-(1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid (0.060 mmol, 25.3 mg), DMAP·pTsOH salt (0.080 mmol, 23.6 mg), and EDC·HCl (0.060 mmol, 11.5 mg). The crude reaction mixture was evaporated to dryness, dissolved in DCM, and loaded onto flash silica gel (approximately 5 g) in a solid loader. The mixture was purified by silica gel flash chromatography (80 g, equilibrated at 100% DCM, eluted at 100% DCM (2 CV) → 10% siRNA / DCM (30 CV)). The fraction containing the product was evaporated to dryness and then triturated with hot methanol. The solid was filtered off and dried in a vacuum oven at approximately 110°C. A bluish solid, 19.8 mg (61% yield), was obtained. MS(APCI): Chemical formula C 103 H 59 BCl2F2N4O 10 Calculated value (M-) = 1630; measured value: 1630. 1 H NMR (400MHz, methylene chloride-d2) δ 8.45~8.34(m,4H), 8.04(d,J=8.1Hz,4H), 7.93~7.84(m,2H), 7.78~7.65(m,10H), 7.61(d,J=8.0Hz,4H), 7. 56~7.46(m,2H), 7.40~7.21(m,12H), 7.12~7.01(m,6H), 7.01~6.92(m,6H), 6.64~6.46(m,5H), 4.03(s,4H).

[0156] Synthesis of compound PLC-13: [ka]

[0157] Compound PLC-13.1 (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 1 L 2N round-bottom flask was placed in an aluminum heat block and a stirring bar was added. A finned condenser / gas adapter, stopper, and flow control valve were attached to the flask. The system was flushed with argon. 6-bromo-1H,3H-benzo[de]isochromene-1,3-dione (40.0 mmol, 11.084 g) and 4-(tert-butyl)-2-nitrophenol (60.0 mmol, 11.712 g) were added to the flask, followed by anhydrous NMP (150 mL). NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg) were added to the flask, followed by anhydrous NMP (25 mL). Under an argon atmosphere, the flask was stirred with a heat block set to 170°C. The reaction mixture was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and 1N HCl (44 mL). The reaction mixture was stirred for 30 minutes, then filtered and washed with water. The precipitate was transferred to a flask containing acetone / DCM, evaporated to dryness, and then azeotropically mixed with toluene. The crude product was dissolved in a small amount of DCM and treated with methanol (300 mL). Part of the DCM and methanol were removed by rotary evaporation using a hot water bath (80°C). Once all the DCM had been removed, the mixture was cooled to room temperature and the solid was filtered off. 8.180 g of a dark-colored powder (52% yield) was obtained. MS(APCI): Chemical formula C 22 H 17 Calculated value for NO6 (M+H) = 392; measured value: 392. 1¹H NMR (400MHz, tetrachloroethane-d2) δ 8.82 (dd, J=8.4, 1.2Hz, 1H), 8.71 (dd, J=7.3, 1.2Hz, 1H), 8.49 (d, J=8.3Hz, 1H), 8.16 (d, J=2.4Hz, 1H), 7.91 (dd, J=8.4, 7.3Hz, 1H), 7.80 (dd, J=8.6, 2.4Hz, 1H), 7.34 (d, J=8.6Hz, 1H), 6.91 (d, J=8.3Hz, 1H), 1.43 (s, 9H).

[0158] Compound PLC-13.2 (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isochromen-1,3-dione): A 250 mL 2N round-bottom flask was placed in an aluminum heat block and a stirring bar was inserted. A finned condenser / gas adapter, stopper, and flow control valve were attached to the flask. The system was flushed with argon. Compound 13.1 (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL) were added to the flask. While stirring at room temperature, HCl (100 mmol, 4.0 N, 25 mL) and SnCl2·2H2O (40.0 mmol, 9.024 g) were added in water. The reaction mixture was stirred for 30 minutes under an argon atmosphere with the heat block set to 90°C. The reaction mixture was cooled to 0°C and made basic with 2N NaOH aqueous solution to pH approximately 8 (pH paper). The solid was separated by slow filtration, and the resulting solid was washed with 2-MeTHF (8 × 100 mL). The filtrate was transferred to a separatory funnel, and the layers were separated. The organic layer was dried over MgSO4, filtered, and evaporated to dryness under vacuum. 3.743 g (quantitative yield) was obtained. It was used in the next step without further purification. MS(APCI): Chemical formula C 22 H 19 Calculated value for NO4 (M+H) = 362; measured value: 362. 1¹H NMR (400MHz, tetrachloroethane-d2) δ 8.88 (dd, J=8.4, 1.2Hz, 1H), 8.69 (dd, J=7.3, 1.2Hz, 1H), 8.48 (d, J=8.4Hz, 1H), 7.89 (dd, J=8.4, 7.3Hz, 1H), 7.03~6.93 (m, 3H), 6.88 (dd, J=8.4, 2.3Hz, 1H), 1.35 (s, 9H).

[0159] Compound PLC-13.3 (9-(tert-butyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A stirring bar, NaNO2 (30.0 mmol, 2.070 g), and water (10 mL) were placed in a 40 mL vial. The vial was stirred in an ice bath at 0°C. Compound 13.2 (4.00 mmol, 1.446 g) was placed in a 100 mL round-bottom flask. Ice AcOH (30 mL) and concentrated HCl (20.0 mmol, 12.1 N, 1.65 mL) were added to the flask. The mixture was stirred at room temperature for several minutes, then placed in an ice bath and stirred for about 1 minute. The NaNO2 solution was added before the acetic acid began to freeze. The NaNO2 was added over about 10 minutes. The diazo solution was stirred at 0°C for 1 hour. A 250 mL 2N round-bottom flask with a large stirring bar was prepared while stirring the diazo solution. A finned condenser and a dropping funnel were attached to the flask. The flask was clamped at an off-center neck, and the dropping funnel was positioned at an off-center neck, so that the solution hit the top of the vortex during stirring. CuSO4·5H2O (27.4 mmol, 6.842 g) and water (80 mL) were added to this flask. About 15 minutes before the diazo solution was obtained, the copper solution was started to heat to 130°C. When the solution reached 130°C, the diazo solution was transferred to the dropping funnel and added dropwise while stirring at high speed for about 30 minutes. After the addition was complete, the solution was heated for a further 1-2 minutes and then cooled in a water bath at room temperature. The precipitate was filtered and washed with water. The precipitate was dried by suction, and then the crude precipitate was dissolved / suspended in DCM and evaporated to dryness on about 10 g of flash silica gel. Purification was performed by silica gel flash chromatography (220 g, solids, equilibration 50% DCM / hexane, elution 50% DCM / hexane (2 CV) → 100% DCM (20 CV) → isocratic DCM (15 CV) → 0% Â / DCM (0 CV) → 1% Â / DCM (10 CV)). Product tail. The fraction containing the product was evaporated to dryness under vacuum. 528 mg (38% yield) was obtained. MS (APCI): Chemical formula C 22 H 16 Calculated value for O4 (M+H) = 345; measured value: 345. 1¹H NMR (400MHz, tetrachloroethane-d2) δ 8.61 (d, J=7.9Hz, 1H), 8.56 (d, J=8.4Hz, 1H), 8.05 (d, J=2.2Hz, 1H), 8.01 (d, J=8.0Hz, 1H), 7.66 (dd, J=8.8, 2.2Hz, 1H), 7.38 (d, J=8.7Hz, 1H), 7.34 (d, J=8.4Hz, 1H), 1.44 (s, 9H).

[0160] Compound PLC-13.4: (4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoic acid): Compound 13.4 was synthesized from Compound 13.3 (1.525 mmol, 525 mg), 4-(4-aminophenyl)butanoic acid (3.05 mmol, 546 mg), and DMAP (0.111 mmol, 14 mg) in the same manner as described above. The crude reaction mixture was diluted with acetone (25 mL) and water (50 mL). The resulting precipitate was filtered and washed 1:1 acetone:water. The resulting solid was dried in a vacuum oven at approximately 110°C. A yellow solid, 738 mg (96% yield) was obtained. MS(APCI): Chemical formula C 32 H 27 Calculated value for NO5 (M+H) = 506; measured value: 506. 1 H NMR(400MHz,DMSO-d6) δ 12.12(s,1H), 8.48~8.29(m,3H), 8.23(d,J=2.3Hz,1H), 7.68(dd,J=8.8,2.3Hz,1H), 7.43~7.30(m,4H ), 7.25(d,J=7.9Hz,2H), 2.75~2.64(m,2H), 2.30(t,J=7.4Hz,2H), 1.88(p,J=7.5Hz,2H), 1.41(s,9H).

[0161] Compound PLC-13((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoate)):PLC-13 is prepared in the same manner as above, 4',4''-(5 It was synthesized from ,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-3,7-diyl)bis([1,1'-biphenyl]-4-ol) (compound PLC-1.4) (0.050 mmol, 39.9 mg), PLC-13.4 (0.150 mmol, 75.8 mg), DMAP·pTsOH salt (0.200 mmol, 58.9 mg), and EDC·HCl (0.150 mmol, 28.8 mg). The crude reaction mixture was diluted 2:1 with hexane and loaded onto approximately 15 g of flash silica gel in a solid loader. The product was purified by silica gel flash chromatography (120 g, solid content, equilibration 40% DCM / hexane, elution 40% DCM / hexane (2 CV) → 100% DCM (10 CV) → isocratic DCM + 1% siRNA modifier). The fraction containing the product was evaporated to dryness under vacuum. The product was triturated with hot MeOH, and the resulting solid was dried in a vacuum oven at approximately 110°C. 78.8 mg of dark red solid (89% yield) was obtained. MS(APCI): Chemical formula C 106 H 83 BF2N4O 10 Calculated value (M-) = 1773; measured value: 1773. 1H NMR(400MHz,tetrachloroethane-d2) δ 8.61(d,J=7.9Hz,2H), 8.56(d,J=8.3Hz,2H), 8.08(d,J=8.3Hz,4H), 8.06(d,J=2.3Hz,2H), 7.99(d,J=8.1Hz,2H), 7.76~7.68(m,8H), 7.63(dd,J=8.7,2.2Hz,2H), 7.47(d,J=8.3Hz,4H), 7.36(d,J=8.7Hz,2H), 7.30(dd,J=8.3,1.7 Hz,6H), 7.26~7.20(m,4H), 7.01~6.94(m,2H), 6.88(t,J=7.5Hz,4H), 6.80(d,J=7.0Hz,4H), 6.57(s,2H), 6.02(s, 2H), 2.89(t,J=7.6Hz,4H), 2.72(t,J=7.4Hz,4H), 2.20(p,J=7.5Hz,4H), 2.01(s,6H), 1.87(s,3H), 1.45(s,18H).

[0162] Synthesis of compound PLC-14: [ka]

[0163] Compound PLC-14.1: (2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): Compound PLC-14.1 was synthesized in the same manner as for Compound 1 from Compound PLC-13.3 (1.191 mmol, 410 mg) and 2-(4-aminophenyl)acetic acid (2.98 mmol, 450 mg) in anhydrous DMF (10 mL). After work-up and precipitation, 579 mg of the product (quantitative yield) was obtained. MS (APCI): Chemical formula C 30 H 23 Calculated value for NO5 (M+H) = 478; measured value: 478. 1H NMR(400MHz,DMSO-d6) δ 8.48(d,J=7.9Hz,1H), 8.44(d,J=8.3Hz,1H), 8.38(d,J=8.1Hz,1H), 8.27(d,J=2.4Hz,1H), 7 .69(dd,J=8.8,2.3Hz,1H), 7.45~7.38(m,4H), 7.31~7.27(m,2H), 3.68(s,2H), 1.41(s,9H).

[0164] Compound PLC-14 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetate): Compound PLC-14 was prepared in the same manner as Compound 2, using 4',4''' -(5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4-ol) (PLC-1.4) (0.050 mmol, 39.9 mg), compound PLC-14.1 (0.150 mmol, 71.6 mg), DMAP·pTsOH salt (0.200 mmol, 58.9 mg), and EDC·HCl (0.150 mmol, 28.8 mg) were used for synthesis. After purification by conventional methods, the product was triturated with hot MeOH. The product was dried in a vacuum oven at approximately 110°C. A dark red solid, 57.3 mg (67% yield) was obtained. MS(APCI): Chemical formula C 102 H 75 BF2N4O 10 The calculated value (M-) for this is 1716; the measured value is 1716. 1H NMR (400MHz, Tactron-d2) δ 8.53(d,J=7.9Hz,2H), 8.48(d,J=8.3Hz,2H), 8.05(d,J=2.3Hz,2H), 8.03~7.98(m,4H), 7.91 (d,J=8.0Hz,2H), 7.75~7.69(m,8H), 7.65~7.58(m,6H), 7.37~7.33(m,4H), 7.32(d,J=8.7Hz ,2H), 7.28~7.23(m,4H), 7.18(d,J=8.3Hz,2H), 7.00~6.93(m,2H), 6.91~6.84(m,4H), 6.84~ 6.78(m,4H), 6.55(s,2H), 6.04(s,2H), 4.03(s,4H), 2.03(s,6H), 1.87(s,3H), 1.45(s,18H).

[0165] Synthesis of compound PLC-15:

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[0166] Compound PLC-15.1((E)-1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)propane-2-en-1-one): A stirring bar, 1-(4-bromophenyl)ethane-1-one (40.0 mmol, 7.960 g), 4-(tert-butyl)benzaldehyde (40.0 mmol, 6.489 g, 6.69 mL), and ethanol (200 proof, 80 mL) were placed in a 500 mL round-bottom flask. KOH (78.4 mmol, 4.399 g) was added while stirring at room temperature. The reaction mixture was vigorously stirred at room temperature. A precipitate formed within 2-3 minutes, so the stirring speed was increased to maintain a stirred slurry. After 30 minutes, TLC showed complete consumption of the starting material. The reaction mixture was poured into 500 mL of stirred water. This mixture was stirred at room temperature for 5 minutes, then the solid was filtered off and washed with water. The precipitate was dried overnight in a vacuum oven at 110°C. Since NMR indicated the presence of impurities, the solid was triturated with methanol. Because this did not improve purity, the material was purified by silica gel column chromatography (330 g, mixture evaporated onto silica gel, equilibrated with 100% hexane, eluted with 100% hexane (2 CV) → 10% siRNA / hexane (20 CV)). The fraction containing the product was evaporated to dryness under vacuum to obtain a grayish-white solid. 8.983 g (65% yield) was obtained. MS(APCI): Chemical formula C 19 H 19 Calculated value for BrO (M+H) = 343; measured value: 343. 1 ¹H NMR (400MHz, tetrachloroethane-d2) δ 7.92~7.85 (m, 2H), 7.79 (d, J=15.6Hz, 1H), 7.70~7.65 (m, 2H), 7.64~7.59 (m, 2H), 7.47 (d, J=8.4Hz, 2H), 7.44 (d, J=15.6Hz, 1H), 1.35 (s, 9H).

[0167] Compound PLC-15.2 (1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)-4-nitrobutan-1-one): A stirring bar was placed in a 250 mL 2N round-bottom flask, and a finned condenser, gas adapter, and flow control valve were attached. After flushing the system with argon, PLC-15.1 (8.898 g, 25.92 mmol), ethanol (200 proof, 27 mL), nitromethane (28 mL), and KOH (5.184 mmol, 291 mg) were added. The reaction mixture was stirred under argon and heated to 95°C in an aluminum heat block. After 30 minutes, TLC showed complete consumption of the starting material. The flask was removed from the heat block and cooled to near room temperature in an ice bath. The reaction mixture was separated into ethyl acetate (100 mL) and water (100 mL), and a small amount of solid NaCl was added to break up the emulsion. The layers were separated, the organic layer was dried over MgSO4, filtered, and concentrated to dryness under vacuum. The resulting yellow oily substance was triturated with hexane while heating to obtain a solid. The solid was stirred overnight at room temperature, then filtered and washed with hexane. The resulting grayish-white solid was dried in a vacuum oven at 80°C. 9.10 g (87% yield) was obtained. MS(APCI): Chemical formula C 20 H 22 Calculated value (M+H) for BrNO3: 404; Measured value: 404. 1 ¹H NMR (400MHz, tetrachloroethane-d2) δ 7.82~7.75 (m, 2H), 7.66~7.59 (m, 2H), 7.37~7.32 (m, 2H), 7.22~7.15 (m, 2H), 4.81 (dd, J=12.5, 6.7Hz, 1H), 4.68 (dd, J=12.5, 8.0Hz, 1H), 4.16 (p, J=7.1Hz, 1H), 3.44 (dd, J=17.9, 6.1Hz, 1H), 3.36 (dd, J=17.9, 7.5Hz, 1H), 1.29 (s, 9H).

[0168] A stirring bar was placed in a 500 mL round-bottom flask containing compound PLC-15.3 (1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)-4,4-dimethoxybutan-1-one). PLC-15.2 (22.51 mmol, 9.10 g) was added to the flask, followed by anhydrous THF (235 mL) and methanol (120 mL). The reaction mixture was vigorously stirred at room temperature, and then KOH (58.35 mmol) was added to the flask. The reaction mixture was stirred at room temperature. In a separate 1 L 2N round-bottom flask, a mixture of H2SO4 (25 mL) and methanol (120 mL) was carefully prepared. The flask was clamped at the off-center neck and carefully stoppered. After 90 minutes, the reaction mixture was added to the addition funnel at the off-center neck. The 1 L flask was cooled in an ice bath at 0°C. The H2SO4 / MeOH mixture was vigorously stirred, and the solution was added dropwise. The mixture appeared to release gas, and the air above the liquid turned a brownish-orange color. The addition was carried out over 2.5 hours. The reaction mixture was stirred for another hour, and then transferred to a 2 L Erlenmeyer flask. Water (300 mL) was added to the stirred mixture, followed by 2N NaOH (approximately 250 mL) to adjust the pH to approximately 10. The solution was separated using DCM (2 × 300 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated to dryness under vacuum. The resulting brown oily substance was allowed to solidify overnight. 1 The 1H NMR spectrum showed a mixture of approximately 75% dimethyl acetal and 25% aldehyde. This mixture was used in the next step without further purification.

[0169] Compound PLC-15.4 (2-(4-bromophenyl)-4-(4-(tert-butyl)phenyl)-1H-pyrrole): A stirring bar was placed in a 100 mL 2N round-bottom flask, and a finned condenser, gas adapter, and flow control were attached. The system was flushed with argon. Crude PLC-15.3 (assuming 100% yield) and NH4OAc (109.4 mmol, 8.432 g) were added to the flask, followed by glacial acetic acid (35 mL). The reaction mixture was stirred under argon and heated in an aluminum heat block at 100 °C. TLC at 5 hours showed complete consumption of the aldehyde and acetal. The reaction mixture was quenched by pouring it into stirred water (300 mL). The resulting precipitate was collected by vacuum filtration and washed with water. It was dried in a vacuum oven at approximately 80 °C. 7.56 g of dark gray solid (95% yield based on compound 1.2) was obtained. MS(APCI):Chemical formula C 20 H 20 Calculated value for BrN (M+H) = 354; measured value: 354. 1 H NMR(400MHz,DMSO-d6) δ 8.49(s,1H), 7.56~7.51(m,2H), 7.51~7.47(m,2H), 7.43~7.37(m,4H), 7.16(dd,J=2.7,1.7Hz,1H), 6.81(dd,J=2.8,1.7Hz,1H), 1.35(s,9H).

[0170] Compound PLC-15.5 (3,7-bis(4-bromophenyl)-1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine): A stirring bar was placed in a 250 mL 2N round-bottom flask, and a finned condenser, gas adapter, and flow control were attached. The system was flushed with argon. PLC-15.4 (2.0 mmol, 709 mg), mesitaldehyde (2.50 mmol, 0.369 mL), and anhydrous dichloroethane (50 mL) were added to the flask. Under an argon atmosphere, nitrogen gas was sprayed onto the reaction mixture for 10 minutes while stirring at room temperature. pTsOH·H2O (0.300 mmol, 57 mg) was added to the flask, and stirring and nitrogen gas spraying were continued for another 10 minutes. The flask was stirred under static argon and heated overnight at 80°C using an aluminum heat block. The reaction mixture was cooled to room temperature, DDQ (1.70 mmol, 386 mg) was added, and stirring continued under argon at room temperature for 1 hour. Et3N (8.00 mmol, 1.11 mL) and BF3·OEt2 (12.0 mmol, 1.48 mL) were added to the reaction mixture. The reaction mixture was stirred at room temperature for 2 minutes, and then the addition of Et3N (8.00 mmol, 1.11 mL) and BF3·OEt2 (12.0 mmol, 1.48 mL) was repeated. The flask was returned to the heat block and the heat block was set to 80°C. The reaction mixture was stirred at 80°C for 90 minutes. The reaction mixture was cooled to room temperature, then doubled in volume by adding hexane, and stirred overnight at room temperature. The reaction mixture was loaded onto 65 g of flash silica gel in a solid loader. Purification was performed by silica gel flash chromatography (330 g, equilibrated with 100% hexane, eluted with 100% hexane (2 CV) → 40% toluene / hexane (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A reddish-pink solid, 236 mg (27% yield), was obtained. MS(APCI): Chemical formula C 50 H 47 Calculated value (M-) for BBr2F2N2: 882; measured value: 882. 1¹H NMR (400MHz, tetrachloroethane-d2) δ 7.84~7.78 (m,4H), 7.64~7.59 (m,4H), 6.89~6.84 (m,4H), 6.69~6.63 (m,4H), 6.45 (s,2H), 6.02 (s,2H), 1.97 (s,6H), 1.88 (s,3H), 1.19 (s,18H).

[0171] Compound PLC-15.6(4',4'''-(1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis(([1,1'-biphenyl]-4-ol))): Compound PLC-15.6 is the same as Compound 10.1 The compound was synthesized in a microwave synthesizer at 110°C from PLC-15.5 (0.205 mmol, 181 mg), (4-hydroxyphenyl)boronic acid (1.228 mmol, 169 mg), K2CO3 (1.228 mmol, 170 mg), and Pd(dppf)Cl2 (0.0512 mmol, 37.4 mg) in THF (8 mL) and water (0.8 mL) using the following method. The crude reaction mixture was loaded onto approximately 65 g of silica gel in a loader. The mixture was purified by silica gel flash chromatography (220 g, equilibrated with 100% toluene, eluted with 100% toluene (2 CV) → 10% siRNA / toluene (20 CV)). The fraction containing the product was evaporated to dryness under vacuum. A dark purple-red solid, 115 mg (62% yield) was obtained. MS(APCI): Chemical formula C 62 H 57 Calculated value (M-) for BF2N2O2: 910; measured value: 910. 1 ¹H NMR (400MHz, tetrachloroethane-d2) δ 7.99~7.90 (m,4H), 7.62~7.54 (m,4H), 7.54~7.47 (m,4H), 6.89~6.82 (m,4H), 6.81~6.75 (m,4H), 6.65~6.56 (m,4H), 6.45 (s,2H), 5.94 (s,2H), 4.94 (s,2H), 1.91 (s,6H), 1.80 (s,3H), 1.11 (s,18H).

[0172] Compound PLC-15((1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoate Compound PLC-15 was synthesized from PLC-15.6 (0.0201 mmol, 18.3 mg), 4-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoic acid (PLC-6.5) (0.0603 mmol, 38.2 mg), DMAP·pTsOH salt (0.0804 mmol, 23.7 mg), and EDC·HCl (0.0804 mmol, 15.4 mg). The crude reaction mixture was loaded onto approximately 25 g of flash silica gel in a loader. The product was purified by silica gel flash chromatography (120 g, solids, equilibrated with 100% hexane, eluted with 100% hexane (3 CV) → 100% DCM / 1% siRNA modifier (0 CV) → 100% DCM / 1% siRNA modifier (15 CV) → 100% DCM / 2% siRNA modifier → 100% DCM / 3% siRNA modifier → 100% DCM / 4% siRNA modifier (tracking the separation of yellow impurities from the product and increasing the siRNA until they eluted separately)). The fraction containing the product was evaporated to dryness under vacuum. A dark red solid, 38.6 mg (90% yield) was obtained. 1H NMR (400MHz, Tactron-d2) δ 8.65(d,J=7.9Hz,2H), 8.59(d,J=8.3Hz,2H), 8.24(d,J=2.2Hz,2H), 8.13~8.04(m,10H), 7.95(s,2H), 7.80(dd,J=8.7,2.1Hz,2H), 7.75~7.69(m,8H), 7.67~7.62(m,4H), 7.56(d, J=8.6Hz,2H), 7.41~7.34(m,6H), 7.30~7.23(m,4H), 6.88(d,J=8.4Hz,4H), 6.70(d,J=8. 2Hz,4H), 6.56(s,2H), 6.03(s,2H), 4.04(s,4H), 2.01(s,6H), 1.89(s,3H), 1.21(s,18H).

[0173] Synthesis of compound PLC-16:

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[0174] Compound PLC-16.1(3,7-bis(4-bromophenyl)-1,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine):PLC-16.1 was prepared in the same manner as described above, using anhydrous DCE (25 mL). It was synthesized from PLC-15.4 (2.0 mmol, 709 mg), 2,6-dichlorobenzaldehyde (1.0 mmol, 175 mg), pTsOH·H2O (0.300 mmol, 57 mg), DDQ (1.30 mmol, 295 mg), Et3N (8.00 mmol, 1.12 mL), and BF3·OEt2 (12.0 mmol, 1.48 mL). The dipyromethane step was carried out at room temperature, not at 80°C. The crude reaction mixture was diluted twice by volume with hexane and loaded onto approximately 60 g of flash silica gel in a loader. Purification was performed by silica gel flash chromatography (330 g, solids content, no equilibration, elution 100% hexane (2 CV) → 50% toluene / hexane (20 CV)). The fraction containing the product was evaporated to dryness under vacuum. A deep reddish-pink solid, 483 mg (53% yield) was obtained. MS(APCI): Chemical formula C 47 H 39 Calculated value (M-) for BBr2Cl2F2N2: 908; measured value: 908. 1 ¹H NMR (400MHz, tetrachloroethane-d2) δ 7.87~7.78 (m,4H), 7.66~7.59 (m,4H), 6.97~6.87 (m,8H), 6.53~6.37 (m,5H), 1.18 (s,18H).

[0175] Compound PLC-16.2(4',4'''-(1,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis(([1,1'-biphenyl]-4-ol))):PLC-16.2 is compound 10. The compound was synthesized in a microwave synthesizer at 110°C from PLC-16.1 (0.205 mmol, 181 mg), (4-hydroxyphenyl)boronic acid (1.228 mmol, 169 mg), K2CO3 (1.228 mmol, 170 mg), and Pd(dppf)Cl2 (0.0512 mmol, 37.4 mg) in THF (8 mL) and water (0.8 mL) using the same method as in 1. The crude reaction mixture was loaded onto approximately 65 g of flash silica in a loader. The mixture was purified by silica gel flash chromatography (220 g, solids content, no equilibration, elution 100% toluene (2 CV) → 10% siRNA / toluene (20 CV)). The fraction containing the product was evaporated to dryness under vacuum. A dark reddish-purple solid, 117 mg (61% yield) was obtained. MS(APCI): Chemical formula C 59 H 49 Calculated value (M-) for BCl2F2N2O2: 936; measured value: 936. 1 H NMR(400MHz,tetrachloroethane-d2) δ 8.08~8.03(m,4H), 7.71~7.66(m,4H), 7.62~7.57(m,4H), 6.94(d,J=7.2Hz,12H), 6.57(s,2H) , 6.51(d,J=1.3Hz,1H), 6.49(s,1H), 6.41(dd,J=9.0,7.0Hz,1H), 5.03(s,2H), 1.19(s,18H).

[0176] Compound PLC-16((1,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl) Compound PLC-16 was synthesized in the same manner as described above from PLC-16.2 (0.030 mmol, 28.1 mg), 4-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)butanoic acid (PLC-6.5) (0.090 mmol, 57 mg), DMAP·pTsOH salt (0.120 mmol, 35.3 mg), and EDC·HCl (0.120 mmol, 23 mg). The crude reaction mixture was diluted with hexane and loaded onto approximately 30 g of flash silica in a loader. The product was purified by silica gel flash chromatography (80 g, equilibrated with 100% hexane / 0.5% siRNA modifier, eluted with 100% hexane / 0.5% siRNA modifier (2 CV) → 100% DCM / 0.5% siRNA modifier (0 CV) → isocratic 100% DCM / 0.5% siRNA modifier (10 CV) → 100% DCM / 1% siRNA modifier (20 CV) → 100% DCM / 2% siRNA modifier (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. The crude product was triturated with hot methanol. The product was dried in a vacuum oven at approximately 110°C. 47.6 mg of a dark red solid (73% yield) was obtained. 1H NMR(400MHz,tetrachloroethane-d2) δ 8.65(d,J=7.8Hz,2H), 8.59(d,J=8.3Hz,2H), 8.24(d,J=2.2Hz,2H), 8.14~8.04(m,10H ), 7.95(s,2H), 7.80(dd,J=8.6,2.1Hz,2H), 7.77~7.69(m,8H), 7.65(d,J=8.3Hz,4H), 7.56(d,J=8.6Hz,2H), 7.37(dd,J=8.3,5.6Hz,6H), 7.30~7.24(m,4H), 6.95(s,8H), 6. 59(s,2H), 6.54~6.48(m,2H), 6.42(dd,J=9.0,7.0Hz,1H), 4.04(s,4H), 1.19(s,18H).

[0177] Synthesis of compound PLC-17: [ka]

[0178] Compound PLC-17.1:2-[4-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid: A mixture of compound PLC-6.3 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol), and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) was degassed at room temperature. The mixture was then heated to 165 °C and held at this temperature for 3 hours. TLC and LC-MS showed approximately 95% conversion without observable side reactions. The mixture was cooled to 50 °C. It was then poured into an acetone solution (40 mL) and pre-cooled in an ice bath. The mixture was held at 0 °C for 2 hours and then stirred overnight at room temperature. The solid was collected by vacuum filtration and washed with acetone (4 mL). Then, it was dried in a vacuum oven at 100°C for 3 hours to obtain the pure compound as a yellowish-brown solid (395.0 mg, 73% yield). MS(APCI): Chemical formula C 26 H 14 Calculated values ​​for BrNO5 ([M+H] + )=500; Measured value: 500. 1H NMR(400MHz,CDCl2CDCl2) δ 8.65(d,J=8.0Hz,1H), 8.62(d,J=8.0Hz,1H), 8.21(dd,J=6.4Hz,2.4Hz,1H), 7.99(bs,1H), 7.95(t,J=7.6Hz ,1H), 7.67(dd,J=8.4Hz,2.4Hz,1H), 7.53(d,J=8.0Hz,2H), 7.37(d,J=8.4Hz,1H), 7.32(m,3H), 2.94(s,2H).

[0179] Compound PLC-17.2:2-[4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid: A stirring bar was attached to a 100 mL vial. Compound PLC-17.1 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2 (41.0 mg, 0.056 mmol), and K2CO3 (298.0 mg, 2.2 mmol) were degassed from the vial in THF / DMF / H2O (22 ml / 4.4 ml / 2.2 ml) at room temperature. The reaction mixture was heated to 80 °C and the reaction was held at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction product was post-treated by adding 0.1N HCl (150 ml) and toluene (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phase was dried over anhydrous Na2SO4, concentrated under a rotary evaporator, and purified by flash chromatography using DCM in toluene (0% → 40%, containing 0.1% TFA) as an eluent to obtain a pure RL-naphthalimide derivative as a yellow / yellowish-brown solid (363.0 mg, 80% yield). MS(APCI): Chemical formula C 33 H 18 Calculated values ​​for F3NO5 ([M+H]) + )=566; Measured value: 566. 1H NMR(400MHz,DMSO-d6) 8.76(m,1H), 8.56(m,2H), 8.52(dd,J=8.0Hz,J=3.2Hz,1H), 8.15(m,2H), 8.06(m,1H), 7.94(d,J=8.0Hz,2H ), 7.66(dd,J=8.0Hz,J=4.0Hz,1H), 7.53(m,1H), 7.45(d,J=8.0Hz,2H), 7.33(d,J=8.0Hz,2H), 3.72(s,2H).

[0180] Compound PLC-17: (1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(1,3-dioxo-9-(trifluoromethyl)-1H-xantheno[2, Compound PLC-17 (1,9-def]isoquinoline-2(3H)-yl(phenyl)acetate) was synthesized from compound PLC-17.2 (0.025 mmol, 22.8 mg), compound PLC-15.6 (0.075 mmol, 37 mg), DMAP·pTsOH salt (0.100 mmol, 29 mg), and EDC·HCl (0.125 mmol, 24 mg) in the same manner as described above. The crude reaction mixture was diluted with hexane and loaded onto approximately 30 g of flash silica gel in a loader. The mixture was purified by silica gel flash chromatography (80 g, solids, equilibrated with 100% hexane, eluted with 100% hexane (2 CV) → 100% DCM (0 CV) → 100% DCM (5 CV) → 100% DCM / 1% siRNA modifier (until the compound was eluted)). The fraction containing the product was evaporated to dryness under vacuum. The product was tritulated with hot methanol. The product was dried in a vacuum oven at approximately 110°C. A dark red solid, 42 mg (91% yield) was obtained. MS(APCI): Chemical formula C 116 H 81 BF8N4O 10 Calculated value (M-) = 1853; measured value: 1853. 1H NMR (400MHz, Tactron-d2) δ 8.54(d,J=7.8Hz,2H), 8.51(d,J=8.3Hz,2H), 8.21(d,J=2.1Hz,2H), 7.98(d,J=8.2Hz,4H), 7.91(d,J=8.1Hz,2H), 7.71(dd,J=8.9,2.0Hz,2H), 7.67~7.59(m,8H), 7.59~7.52(m,4H), 7 .41(d,J=8.6Hz,2H), 7.31~7.24(m,6H), 7.21~7.14(m,4H), 6.83~6.76(m,4H), 6.61(d,J=8 .3Hz,4H), 6.46(s,2H), 5.94(s,2H), 3.95(s,4H), 1.92(s,6H), 1.80(s,3H), 1.11(s,18H).

[0181] Synthesis of compound PLC-18:

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[0182] Compound PLC-18.1 (2-[4-(9-(4-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): Compound PLC-18.1 was prepared in the same manner as compound 2.3 in THF (60 mL), DMF (12 mL), and water (6 mL) as compound PLC-17. The compound was synthesized from 1(2.00 mmol, 1001 mg), 2-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.00 mmol, 1465 mg), K2CO3 (5.50 mmol, 760 mg), and Pd(dppf)Cl2 (0.140 mmol, 102 mg) over 2 hours at 80°C. The crude product reaction was quenched with 6N HCl (5 mL) and diluted with water (50 mL) and THF (50 mL). Sodium chloride was added until the aqueous layer was saturated, then the layers were separated and extracted with THF (3 × 50 mL). The combined organic layers were washed with brine (50 mL), dried over MgSO4, filtered, and evaporated to dryness under vacuum (including DMF). The crude product was evaporated onto approximately 50 g of flash silica gel and placed in a loader. Purification was performed by silica gel flash chromatography (220 g, solid content, equilibrated 100% DCM, eluted 100% DCM (2 CV) → 40% (Âx / 0.1% TFA) / DCM (20 CV) → 70% (Âx / 0.1% TFA) / DCM (20 CV)). The fraction containing the product was evaporated to dryness under vacuum. A yellow solid, 722 mg (55% yield), was obtained. MS (APCI): Chemical formula C 39 H 33 Calculated value for NO9 (M+H) = 660; measured value: 660. 1H NMR(400MHz,DMSO-d6) δ 8.57(d,J=2.2Hz,1H)、8.52(s,2H)、8.48(d,J=8.3Hz,1H)、7.90(dd,J=8.7,2.2Hz,1H)、7.84~7.78(m,2H)、7.55(d,J=8.7Hz,1H)、7.48(d,J=8.3Hz,1H)、7.41(d,J=8.1Hz,2H)、7.33~7.26(m,2H)、7.12~7.07(m,2H)、4.22~4.14(m,2H)、3.82~3.76(m,2H)、3.68(s,2H)、3.65~3.59(m,2H)、3.58~3.51(m,4H)、3.48~3.41(m,2H)、3.25(s,3H)。

[0183] Compound PLC-18((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetate): Compound PLC-18 is used as described above. The compound was synthesized in the same manner as described above, from 4',4'''-(5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4-ol) (PLC-1.4, 0.040 mmol, 32 mg), compound PLC18.1 (0.120 mmol, 79.2 mg), DMAP·pTsOH salt (0.160 mmol, 47.1 mg), and EDC·HCl (0.200 mmol, 38.3 mg). The crude product was loaded onto approximately 65 g of flash silica gel in a loader. The product was purified by silica gel flash chromatography (120 g, solids content, equilibrated with 100% DCM, elution 100% DCM (2 CV) → 100% DCM / 0.5% MeOH modifier (1 CV) → 100% DCM / 1% MeOH modifier (1 CV) → 100% DCM / 2% MeOH modifier (20 CV) → 100% DCM / 3% MeOH modifier (5 CV)). The product eluted too slowly with 2% MeOH, but rapidly with 3% MeOH modifier. The fraction containing the pure product was evaporated to dryness under vacuum. A dark red powder, 40.8 mg (52.8% yield) was obtained. MS (APCI): Chemical formula C 120 H 95 BF2N4O 18 The calculated value for (M-) is 1929; the measured value is 1929. 1H NMR(400MHz,tetrachloroethane-d2) δ 8.61(d,J=7.8Hz,2H), 8.56(d,J=8.3Hz,2H), 8.18(d,J=2.2Hz,2H), 8.08(d,J=8.2Hz,4H), 8.00(d,J=8.2Hz,2H), 7.79~7.68(m ,10H), 7.64(t,J=8.5Hz,8H), 7.46(d,J=8.6Hz,2H), 7.41~7.35(m,4H), 7.31(d,J=8.4Hz,2H), 7.29~7.24(m,4H), 7.12~7.04(m, 4H), 6.97(t,J=7.2Hz,2H), 6.88(t,J=7.5Hz,4H), 6.80(d,J=7.1Hz,4H), 6.57(s,2H), 6.02(s,2H), 4.22(t,J=4.8Hz,4H), 4.04 (s,4H), 3.90(t,J=4.8Hz,4H), 3.78~3.72(m,4H), 3.72~3.62(m,8H), 3.59~3.53(m,4H), 3.38(s,6H), 2.02(s,6H), 1.87(s,3H).

[0184] Synthesis of compound PLC-19: [ka]

[0185] Compound PLC-19.1: ((E)-1-(4-bromophenyl)-3-(4-octylphenyl)propane-2-en-1-one): Compound PLC-19.1 was synthesized at room temperature from 1-(4-bromophenyl)ethane-1-one (22.9 mmol, 4.557 g), 4-octylbenzaldehyde (22.9 mmol, 5.00 g), and KOH (44.89 mmol, 2.519 g) in 200 proof EtOH (35 mL), in the same manner as described above. The crude product was precipitated with water, filtered, and recrystallized from 200 proof EtOH. A grayish-white solid, 8.197 g (90% yield) was obtained. MS(APCI): Chemical formula C 23 H 27 Calculated value for BrO (M+H) = 399; measured value: 399. 1H NMR(400MHz,TCE) δ 7.91~7.85(m,2H), 7.79(d,J=15.6Hz,1H), 7.70~7.64(m,2H), 7.61~7.55(m,2H), 7.44(d,J=15.7Hz, 1H), 7.29~7.23(m,2H), 2.70~2.60(m,2H), 1.66~1.61(m,2H), 1.39~1.20(m,10H), 0.92~0.86(m,3H).

[0186] Compound PLC-19.2 (1-(4-bromophenyl)-4-nitro-3-(4-octylphenyl)butan-1-one): Compound PLC-19.2 was synthesized in the same manner as described above from compound PLC-19.1 (20.52 mmol, 8.197 g) and KOH (4.104 mmol, 230 mg) in nitromethane (22 mL) and 200-proof ethanol (22 mL) at 95°C for 1 hour. The crude reaction mixture was separated between 100 mL of water and 100 mL of ELISA. A small amount of NaCl disrupted the emulsion. The layers were separated, the organic layer was dried over MgSO4, filtered, and evaporated to dryness under vacuum. A dark brown oily substance, 9.34 g (99% yield) was obtained. MS(APCI): Chemical formula C 24 H 30 Calculated value (M+H) for BrNO3: 460; Measured value: 460. 1 H NMR(400MHz,TCE) δ 7.81~7.74(m,2H), 7.67~7.59(m,2H), 7.16(s,4H), 4.81(dd,J=12.4,6.6Hz,1H), 4.67(dd,J=12.5,8.0Hz,1H), 4.15(p,J=6.8Hz,1H), 3 .43(dd,J=17.9,6.2Hz,1H), 3.36(dd,J=17.9,7.5Hz,1H), 2.62~2.51(m,2H), 1.61~1.50(m,4H), 1.38~1.22(m,10H), 0.94~0.84(m,3H).

[0187] Compound PLC-19.3 (1-(4-bromophenyl)-4,4-dimethoxy-3-(4-octylphenyl)butan-1-one): Compound PLC-19.3 was synthesized from compound PLC-19.2 (20.29 mmol, 9.34 g) and KOH (52.54 mmol, 2.948 g) in dry THF (225 mL) and dry MeOH (115 mL) in the same manner as described above. This solution was added dropwise to a solution of 95% H2SO4 (25 mL) in dry MeOH (120 mL) at 0°C. After workup and evaporation of all solvent under vacuum, a brown oily substance, 8.13 g (82% yield), was obtained. A mixture of dimethyl acetal and aldehyde. MS(APCI): Chemical formula C 26 H 35 Calculated value (M+H) for BrO3: 475; Measured value: 475.

[0188] Compound PLC-19.4 (2-(4-bromophenyl)-4-(4-octylphenyl)-1H-pyrrole): Compound PLC-19.4 was synthesized at 100°C from compound PLC-19.3 (20.29 mmol, assumed to be 100% from the previous step) and NH4OAc (109.4 mmol, 8.432 g) in AcOH (35 mL) in the same manner as described above. After heating overnight at 100°C, the reaction mixture was cooled to room temperature and water was added. The resulting precipitate was filtered off, dissolved in DCM, dried over MgSO4, and evaporated to dryness. The product was recrystallized from 200 proof ethanol. A purple-blue solid, 3.652 g (41% yield) was obtained. MS(APCI): Chemical formula C 24 H 28 Calculated value for BrN (M+H) = 410; measured value: 410. 1 H NMR(400MHz,TCE) δ 8.49(s,1H), 7.56~7.50(m,2H), 7.50~7.44(m,2H), 7.43~7.37(m,2H), 7.19(d,J=8.3Hz,2H), 7.15(t,J=2.1Hz ,1H), 6.81(dd,J=2.6,1.6Hz,1H), 2.66~2.56(m,2H), 1.70~1.56(m,4H), 1.42~1.21(m,8H), 0.94~0.83(m,3H).

[0189] Compound PLC-19.5 (3,7-bis(4-bromophenyl)-5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine): Compound PLC-19.5 was prepared in the same manner as above, by adding compound PLC-19.4 (2.10 mmol) to dried DCE (20 mL). The compound was synthesized from 862 mg of 2,4,6-trimethylbenzaldehyde (1.00 mmol, 0.148 mL), and pTsOH·H2O (0.400 mmol, 76 mg), then DDQ (1.700 mmol, 386 mg), 2×Et3N (8.00 mmol, 1.11 mL), and BF3·OEt2 (12.00 mmol, 1.50 mL) at 60°C followed by 50°C. The crude reaction mixture was diluted with hexane (approximately 250 mL) and washed with 6N HCl (50 mL), water (50 mL), saturated NaHCO3 (2 × 100 mL), and brine (50 mL). The organic layer was dried over MgSO4, filtered, and evaporated to dryness under vacuum. The crude material was dissolved in hexane and loaded onto 65 g of silica gel in a loader. The product was purified by silica gel flash chromatography (220 g, solid content, equilibrated with 100% hexane, eluted with 100% hexane (2 CV) → 30% siRNA / hexane (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A deep red solid, 512 mg (51% yield) was obtained. MS (APCI): Chemical formula C 58 H 63 Calculated value (M+H) for BBr2F2N2: 995; Measured value: 995. 1 H NMR(400MHz,TCE) δ 7.83~7.76(m,4H), 7.66~7.57(m,4H), 6.68(d,J=8.2Hz,4H), 6.64(d,J=8.1Hz,4H), 6.43(s,2H), 6.04(s,2H) , 2.46~2.35(m,4H), 1.97(s,6H), 1.89(s,3H), 1.44(p,J=6.8Hz,4H), 1.38~1.21(m,22H), 0.95~0.86(m,6H).

[0190] Compound PLC-19.6(4',4'''-(5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-3,7-diyl)bis([1,1'-biphenyl]-4-ol)): Compound PLC-19.6 is prepared in the same manner as described above, using THF (10 mL) and water (2 mL). The compound PLC-19.5 (0.200 mmol, 200 mg), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (0.800 mmol, 176 mg), K2CO3 (4.60 mmol, 636 mg), and Pd(dppf)Cl2 (0.020 mmol, 15 mg) were synthesized in a microwave synthesizer at 110°C for 3 hours. THF and water were evaporated under vacuum, the reaction mixture was dissolved in DCM, and loaded onto approximately 40 g of silica gel in a loader. Purification was performed by silica gel flash chromatography (220 g, solids, equilibration 0% siRNA / hexane, elution 0% (2 CV) → 5% EtOAC / hexane (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A dark red solid, 99 mg (48% yield) was obtained. MS (APCI): Chemical formula C 70 H 73 Calculated value for BF2N2O2: (M+H) = 1023; measured value: 1023. 1 H NMR(400MHz,TCE) δ 8.08~7.98(m,4H), 7.71~7.62(m,4H), 7.62~7.54(m,4H), 6.98~6.89(m,4H), 6.73~6.64(m,8H), 6.52(s,2H), 6.05(s,2H), 4. 98(s,2H), 2.41(dd,J=8.8,6.7Hz,4H), 2.00(s,6H), 1.90(s,3H), 1.53~1.39(m,4H), 1.38~1.26(m,20H), 0.96~0.87(m,6H).

[0191] Compound PLC-19: ((5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline- Compound 42 (2(3H)-yl)phenyl)acetate) was synthesized in the same manner as for compound 36 from compound 42.1 (0.0400 mmol, 41 mg), compound 36.4 (0.120 mmol, 68 mg), DMAP·pTsOH salt (0.160 mmol, 47 mg), and EDC·HCl (0.240 mmol, 46 mg) combined in a 40 mL screw-cap vial containing a stirring bar and dry DCM (10 mL), using the same method as for compound 36. The crude product was loaded onto approximately 20 g of silica gel in a loader. The product was purified by silica gel flash chromatography (120 g, solids content, equilibration 0% siRNA / DCM, elution 0% (2 CV) → 10% siRNA / DCM (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A deep red solid, 52 mg (61% yield) was obtained. 1 H NMR(400MHz,TCE) δ 8.63(d,J=7.8Hz,2H), 8.58(d,J=8.3Hz,2H), 8.23(d,J=2.3Hz,2H), 8.07(d,J=8.2Hz,4H), 8.02(d,J=8.1H) z,2H), 7.83~7.75(m,10H), 7.75~7.69(m,8H), 7.65(d,J=8.4Hz,4H), 7.52(d,J=8.6Hz,2H), 7.41~7.36(m,4 H), 7.34(d,J=8.3Hz,2H), 7.26(d,J=8.6Hz,4H), 6.75~6.63(m,8H), 6.54(s,2H), 6.05(s,2H), 4.04(s,4H), 2.42(t,J=7.7Hz,4H), 2.01(s,6H), 1.91(s,3H), 1.51~1.39(m,4H), 1.37~1.25(m,20H), 0.95~0.88(m,6H).

[0192] Synthesis of compound PLC-20 [ka]

[0193] Compound PLC-20.1:(4',4'''-(5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-3-ol)): Compound PLC-20.1 was synthesized in the same manner as described above, from compound PLC-19.5 (0.200 mmol, 200 mg), (3-hydroxyphenyl)boronic acid (0.800 mmol, 110 mg), K2CO3 (4.60 mmol, 636 mg), and Pd(dppf)Cl2 (0.020 mmol, 15 mg) in THF (10 mL) and water (2 mL) over 3 hours at 110°C in a microwave synthesizer. THF and water were evaporated under vacuum, the reaction mixture was dissolved in DCM, and loaded onto approximately 40 g of silica gel in a loader. The mixture was purified by silica gel flash chromatography (220 g, solid content, equilibrated with 0% siRNA / hexane, eluted 0% (2 CV) → 5% EtOAC / hexane (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A dark red solid, 101 mg (49% yield), was obtained. MS (APCI): Chemical formula C 70 H 73 Calculated value for BF2N2O2: (M+H) = 1023; measured value: 1023. 1 1H NMR (400MHz, TCE) δ 7.95(d,J=8.3Hz,4H), 7.66~7.54(m,4H), 7.26(t,J=7.9Hz,2H), 7.17(dt ,J=7.9,1.2Hz,2H), 7.05(t,J=2.0Hz,2H), 6.76(ddd,J=8.0,2.6,1.0Hz,2 H), 6.64~6.54(m,8H), 6.44(s,2H), 5.96(s,2H), 4.86(s,2H), 2.32(t,J=7 .8Hz,4H), 1.43~1.29(m,4H), 1.19(d,J=16.2Hz,20H), 0.87~0.78(m,6H).

[0194] Compound PLC-20: ((5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',3-diyl)bis(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H Compound PLC-20 was synthesized in the same manner as described above, from compound PLC20.1 (0.0400 mmol, 41 mg), compound PLC-17.2 (0.140 mmol, 79 mg), DMAP·pTsOH salt (0.160 mmol, 47 mg), and EDC·HCl (0.240 mmol, 46 mg) combined in a 40 mL screw-cap vial containing a stirring bar and dry DCM (10 mL). The crude product was loaded onto approximately 40 g of silica gel in a loader. Purification was performed by silica gel flash chromatography (220 g, solids content, equilibration 0% siRNA / DCM, elution 0% (2 CV) → 10% siRNA / DCM (30 CV)). The fraction containing the product was evaporated to dryness under vacuum. A deep red solid, 47 mg (55% yield) was obtained. 1 H NMR(400MHz,TCE) δ 8.61(d,J=7.9Hz,2H), 8.57(d,J=8.3Hz,2H), 8.21(d,J=2.2Hz,2H), 8.08(d,J=8.2Hz,4H), 8.00(d,J=8.2Hz,2H) ), 7.82~7.72(m,14H), 7.63(d,J=8.3Hz,4H), 7.59(d,J=7.9Hz,2H), 7.52~7.44(m,6H), 7.40~7.35(m,4H), 7.33 (d,J=8.3Hz,2H), 7.14(ddd,J=8.0,2.3,1.0Hz,2H), 6.74~6.63(m,8H), 6.54(s,2H), 6.05(s,2H), 4.04(s,4H), 2.41(t,J=7.8Hz,4H), 2.00(s,6H), 1.90(s,3H), 1.53~1.39(m,4H), 1.37~1.26(m,20H), 0.91(t,J=6.7Hz,6H).

[0195] Synthesis of compound PLC-21: [ka]

[0196] Compound PLC-21.1:2-[4-[9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid: A stirring bar was attached to a 100 mL vial. Compound PLC-17.1 (400.0 mg, 0.80 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2 (41.0 mg, 0.056 mmol), and K2CO3 (412.6 mg, 2.2 mmol) were degassed at room temperature from THF / DMF / H2O (22 ml / 4.4 ml / 2.2 ml) in the vial. The reaction mixture was heated to 80 °C and the reaction was held at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction product was post-treated by adding 0.1N HCl (150 ml) and toluene (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phase was dried over anhydrous Na2SO4, concentrated under a rotary evaporator, and purified by flash chromatography using DCM in toluene (0% → 40%, containing 0.1% TFA) as an eluent to obtain pure RL-naphthalimide derivative PLC-21.1 as a yellow / yellowish-brown solid (311.0 mg, 61% yield). MS(APCI): Chemical formula C 34 H 17 Calculated values ​​for F6NO5 ([M+H]) + )=634; Measured value: 634. 1 H NMR(400MHz,DMSO-d6) 8.73(m,1H), 8.46(m,5H), 8.10(m,2H), 7.57(m,1H), 7.42(d,J=8.0Hz,2H), 7.40(m,1H), 7.30(d,J=8.0Hz,2H), 3.72(s,2H).

[0197] Compound PLC-21: A stirring bar was attached to a 25 mL vial. Compound PLC-1.4 (40.0 mg, 0.05 mmol), compound PLC-21.1 (158.4 mg, 0.25 mmol), EDC·HCl (76.7 mg, 0.40 mmol), and DMAP·TsOH (75.0 mg, 0.25 mmol) were added to the vial, followed by the addition of anhydrous DCM (4 ml). The reaction mixture was kept at room temperature for 48 hours. After the reaction was complete, the mixture was loaded onto silica gel and purified by flash chromatography using DCM in  (0% → 4%) as the eluent to provide pure RL-naphthalimide-BODIPY compound PLC-21 as a dark purple solid. The solid was further triturated with  (1 mL) and MeOH (20 ml) to obtain RL-naphthalimide-BODIPY 1605-108 (60.0 mg, 60% yield). MS(APCI): This could not be observed with the inventors' LCMS system. 1 H NMR(400MHz,CDCl2CDCl2) 8.65(d,J=8.0Hz,2H), 8.59(d,J=8.0Hz,2H), 8.24(d,J=2.4Hz,2H), 8.08(m,10 H), 7.95(s,2H), 7.80(dd,J=8.0Hz,2.4Hz,2H), 7.73(m,8H), 7.65(m,4H), 7.56 (d,J=8.0Hz,2H), 7.38(m,6H), 7.26(m,4H), 6.97(m,2H), 6.88(t,J=8.0Hz,4H) , 6.79(m,4H), 6.57(s,2H), 6.02(s,2H), 4.04(s,4H), 2.01(s,6H), 1.87(s,3H).

[0198] Synthesis of compound PLC-22: [ka]

[0199] Compound PLC-22.1: (9-bromo-2-(5-hydroxypentyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione). Compound PLC-6.3 (1.223 g, 3.33 mmol, 1 equivalent) was suspended in 35 mL of anhydrous DMSO, and 5-amino-1-pentanol (1.5 g, 20.0 mmol, 6 equivalents) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 160 °C for 45 minutes, and LMCMS indicated that the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL), then MeOH (100 mL), and dried in a vacuum oven to obtain 1.2 g of a greenish-yellow solid (85% yield). MS(APCI):C 23 H 18 Calculated value (M-) for BrNO4: 453; measured value: 453. MS(APCI): Chemical formula C 23 H 18 Calculated value (M-) for BrNO4: 452; Measured value: 452. 1 H NMR(400MHz) δ 8.52(d,J=7.8Hz,1H), 8.48(d,J=8.3Hz,1H), 8.09(d,J=2.3Hz,1H), 7.82(d,J=8.0Hz,1H), 7.54(dd,J=8.8,2.3Hz,1H), 7.23(d,J=8.3Hz,1H) ), 7.19(d,J=8.8Hz,1H), 4.14~4.02(m,2H), 3.64~3.49(m,2H), 1.68(p,J=7.7Hz,2H), 1.60~1.54(m,2H), 1.41(q,J=8.0Hz,2H), 1.28(s,1H).

[0200] Compound PLC-22.2: (2-(5-hydroxypentyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-22.1 (1.13 g, 2.5 mmol, 1 equivalent) was suspended in DMF (10 ml) and H2O (5 ml), and 4-(trifluoromethyl)benzeneboronic acid (0.949 g, 5.0 mmol, 2 equivalents), K2CO3 (0.691 g, 5.0 mmol, 2 equivalents), and Pd(dppf)Cl2·DCM (40.8 mg, 0.05 mmol, 0.02 equivalents) were added. The mixture was degassed three times by a Vac-Fill argon cycle and heated and stirred at 90°C for 5 hours. The reaction mixture was cooled to room temperature and water was added. The resulting mixture was held at room temperature for 12 hours. The greenish-yellow solid was filtered, washed with water, and then washed with MeOH to obtain 1.24 g of greenish-yellow solid (95% yield). MS(APCI): Chemical formula C 30 H 22 Calculated value (M-) for F3NO4: 517; Measured value: 517. 1 1H NMR (400MHz) δ 8.56(d,J=7.9Hz,1H), 8.51(d,J=8.3Hz,1H), 8.17(d,J=2.1Hz,1H), 7.97( d,J=8.0Hz,1H), 7.69(dd,J=10.3,1.9Hz,4H), 7.42(d,J=8.6Hz,1H), 7.28( d,J=8.3Hz,1H), 4.09(t,J=7.5Hz,2H), 3.57(q,J=6.2Hz,2H), 1.69(p,J=7 .8Hz,2H), 1.61~1.54(m,2H), 1.42(q,J=8.0Hz,2H), 1.28(t,J=5.5Hz,1H).

[0201] Compound PLC-22.3: (2-(5-bromopentyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A mixture of PLC-22.2 (0.66 g, 1.288 mmol) and 48% aqueous HBr (20.0 ml) was refluxed under heat blocking at 120°C for 5 hours with stirring (HBr 48% bp: 126°C). After cooling to room temperature, the mixture was poured into ice water, the solid was filtered, washed with water, and dried in a vacuum oven to obtain 82% of the desired compound containing unreacted SM. 0.7 g of a greenish-yellow solid (93% yield) was obtained. The product was used in the next step without further purification. MS(APCI): Chemical formula C 30 H 21 Calculated value (M-) for BrF3NO3: 581; Measured value: 581. 1 H NMR(400MHz) δ 8.57(d,J=7.9Hz,1H), 8.51(d,J=8.3Hz,1H), 8.18(d,J=2.2Hz,1H), 7.98(d,J=7.9Hz,1H), 7.69(dd,J=9.6,2.0Hz,4H), 7.43( d,J=8.6Hz,1H), 7.28(d,J=8.3Hz,1H), 4.09(t,J=7.5Hz,3H), 3.38(t,J=6.7Hz,2H), 1.97~1.81(m,2H), 1.69(t,J=7.8Hz,2H).

[0202] Compound PLC-22:2'-(5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4l) 4 ,5l 5-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl))bis(oxy))bis(pentane-5,1-diyl))bis(9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione). Compound 22.3 (7.625 mg, 0.15 mmol, 3 equivalents) was suspended in anhydrous DCM (10.0 ml), compound 1.4 (39.93 mg, 0.05 mmol, 1 equivalent) and K2CO3 (20.73 mg, 0.15 mmol, 3 equivalents) were added, and the mixture was stirred at 65°C for 45 minutes under an argon atmosphere. The mixture was concentrated to dryness, the solid was washed with 50 ml of water, dissolved in DCM, loaded onto an 80 g SiO2 column, and eluted with Hex-DCM(1 / 1), DCM alone, and then with 0.5% EA in DCM. The mixture was washed with MeOH to obtain a yield of 82 mg, 94%. 1 H NMR(400MHz) δ 8.50(d,J=7.9Hz,2H), 8.45(d,J=8.3Hz,2H), 8.10(d,J=2.1Hz,2H), 7.94(d,J=8.2Hz,4H), 7.90(d,J= 8.1Hz,2H), 7.68(s,7H), 7.65(dd,J=8.6,2.2Hz,2H), 7.58(d,J=8.4Hz,4H), 7.50(d,J=8.7Hz,4H), 7. 37(d,J=8.6Hz,2H), 7.21(d,J=8.3Hz,2H), 6.88(t,J=8.0Hz,6H), 6.79(t,J=7.5Hz,4H), 6.69(d,J=7. 1Hz,4H), 6.46(s,2H), 4.11(t,J=7.4Hz,4H), 3.95(t,J=6.4Hz,4H), 1.91(s,6H), 1.88~1.68(m,11H).

[0203] Example 3: Manufacturing of color conversion film The glass substrate was prepared in essentially the following manner: A 1.1 mm thick glass substrate measuring 1 inch x 1 inch was cut to size. Next, the glass substrate was washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for approximately 1 hour. Next, the glass was immersed in isopropanol (IPA) and sonicated for approximately 1 hour. Next, the glass substrate was immersed in acetone and sonicated for approximately 1 hour. Finally, the glass was removed from the acetone bath and dried with nitrogen gas at room temperature.

[0204] A 20 wt% solution of poly(methyl methacrylate) (PMMA) copolymer (average molecular weight 120,000 according to GPC, manufactured by MilliporeSigma, Burlington, Massachusetts, USA) in cyclopentanone (99.9% purity) was prepared. The prepared copolymer was stirred overnight at 40°C. (PMMA) CAS: 9011-14-7, (cyclopentanone) CAS: 120-92-3.

[0205] The 20% PMMA solution (4 g) prepared above was added to 3 mg of the photoluminescence complex prepared as described above in a sealed container and mixed for approximately 30 minutes. Next, the PMMA / Lumiphore solution was spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds, followed by 500 RPM for 5 seconds. The resulting wet coating had a thickness of approximately 10 μm. The sample was covered with aluminum foil before spin-coating to protect it from exposure. Three samples were prepared in this manner, one for emission / FWHM and the other for quantum yield. The spin-coated samples were baked in a vacuum oven at 80°C for 3 hours to evaporate the remaining solvent.

[0206] A 1-inch x 1-inch sample was inserted into a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, Maryland, USA). All device operations were performed in a nitrogen-filled glove box. The absorption / emission spectrum obtained for PLC-1 is shown in Figure 1. The absorption / emission spectrum obtained for PLC-2 is shown in Figure 2. The absorption / emission spectrum obtained for PLC-4 is shown in Figure 3. The absorption / emission spectrum obtained for PLC-5 is shown in Figure 4.

[0207] The fluorescence spectra of the 1-inch x 1-inch film samples prepared as described above were determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, New Jersey, USA) with excitation wavelengths set to their respective maximum absorbance wavelengths. The maximum emission and FWHM are shown in Table 1.

[0208] The quantum yield of the 1-inch x 1-inch sample prepared as described above was determined by exciting it at its respective maximum absorption wavelength using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell, California, USA). The results are reported in Table 1.

[0209] The results of the film characterization (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1 below.

[0210] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] Table 6 Table 7

Claims

1. A photoluminescent complex, Blue light absorbing xanthenoizoquinoline derivative, Linker complex and The boron-dipyromethene (BODIPY) moiety, Includes, The linker complex covalently bonds the xanthenoizoquinoline derivative and the BODIPY moiety, the photoluminescent complex absorbs light energy of a first excitation wavelength and emits light energy of a second, higher wavelength, and the photoluminescent complex has an emission quantum yield of more than 80%. The following structure: 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 A photoluminescent complex that is one of the following.

2. It is a color conversion film, A transparent substrate layer, A color conversion layer containing a resin matrix, The photoluminescent complex according to claim 1 is dispersed in the resin matrix, Color conversion film, including

3. The color conversion film according to claim 2, wherein the film has a thickness of 10 μm to 200 μm.

4. The color conversion film according to claim 2, wherein the film absorbs light in the wavelength range of 400 nm to 480 nm and emits light in the wavelength range of 575 nm to 645 nm.

5. A method for producing a color conversion film according to claim 2, 3, or 4, Dissolving the photoluminescent complex and binder resin in a solvent, The mixture is applied to one of the opposing surfaces of the transparent substrate, Methods that include...

6. A backlight unit comprising the color conversion film according to claim 2, 3, or 4.

7. A display device including the backlight unit described in claim 6.

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